Thiadiazole compound and use thereof

ABSTRACT

The thiadiazole compound represented by the formula (A):  
                 
 
wherein R 1  represents a C1-C7 alkyl group, a C3-C7 alkenyl group, a C3-C7 alkynyl group and the like; R2 represents a C1-C4 alkyl group substituted with a hetero ring group in which the hetero ring group may be substituted, which the hetero ring group is a five-membered ring containing only an oxygen atom(s) or a sulfur atom(s) as a hetero atom(s); 
has an excellent arthropod pests controlling activity.

FIELD OF THE INVENTION

The present invention relates to a thiadiazole compound and use thereof.

BACKGROUND ARTS

It is known that a kind of thiadiazole compound can be used as an activeingredient of a arthropod pests controlling composition (DE3030661publication).

However, the arthropod pests controlling activity of this thiadiazolecompound is not always enough, then it is desired new compounds havingmore efficient arthropod pests controlling activity.

DISCLOSURE OF THE INVENTION

The present inventor has earnestly studied, and as a result, found outthat the thiadiazole compounds shown by the formula (A) described belowhave an excellent arthropod pests controlling activity, therebycompleting the present invention.

Namely, the present invention relates to a thiadiazole compound shown bythe formula (A) (hereinafter, referred as the compound of the presentinvention):

wherein, in the formula,

-   R¹ represents a C1-C7 alkyl group, a C3-C7 alkenyl group, a C3-C7    alkynyl group, a C2-C7 alkoxyalkyl group, a C2-C7 alkylthioalkyl    group, a C4-C7 alkoxyalkoxyalkyl group, a C4-C7 alkylthioalkoxyalkyl    group, a phenyl group in which the phenyl group may be substituted,    a C1-C2 alkyl group substituted with a phenyl group in which the    phenyl group may be substituted, a C1-C2 alkyl group substituted    with a phenoxy group in which the phenoxy group may be substituted,    a C2-C3 alkoxyalkyl group substituted with a phenyl group in which    the phenyl group may be substituted, or the formula (B):    wherein R³ represents a C1-C3 alkyl group, R⁴ represents a hydrogen    atom, a methyl group, an ethyl group, a propyl group, or a phenyl    group in which the phenyl group may be substituted; and R²    represents a C1-C4 alkyl group substituted with a hetero ring group    in which the hetero ring group may be substituted, which the hetero    ring group is a five-membered ring containing only an oxygen atom(s)    or a sulfur atom(s) as a hetero atom(s); a arthropod pests    controlling composition comprising the compound of the present    invention as an active ingredient, and a method for controlling    arthropod pests comprising applying an effective amount of the    compound of the present invention to arthropod pests or habitat    arthropod pests.

In the compound of the present invention, each of the substituent shownby R¹ or R² is specifically exemplified below.

The C1-C7 alkyl group represented by R¹ includes, for example, methylgroup, ethyl group, propyl group, isopropyl group, butyl group,sec-butyl group and tert-butyl group.

The C3-C7 alkenyl group represented by R¹ includes, for example,allylgroup, 2-butenylgroup, 3-methyl-2-butenylgroup and 2-pentenylgroup.

The C3-C7 alkynyl group represented by R¹ includes, for example,2-propynyl group, 1-methyl-2-propynyl group, 2-butynyl group, 3-butynylgroup, and 2-pentynyl group.

The C2-C7 alkoxyalkyl group represented by R¹ includes, for example,(C1-C6 alkoxy) methyl group; more specifically, methoxymethyl group,ethoxymethyl group, propoxymethyl group and isopropoxymethyl group.

The C2-C7 alkylthioalkyl group represented by R¹ includes, for example,(C1-C6 alkylthio) alkyl group; more specifically, methylthiomethylgroup, ethylthiomethyl group, propothiomethyl group andisopropylthiomethyl group.

The C4-C7 alkoxyalkoxyalkyl group represented by R¹ includes, forexample, methoxyethoxymethyl group.

The C4-C7 alkylthioalkoxyalkyl group represented by R¹ includes, forexample, ethylthioethoxymethyl group.

The phenyl group, in which the phenyl group may be substituted,represented by R¹ includes, for example, the phenyl group in which thephenyl group may be substituted with one or more selected from the groupconsisting of C1-C4 alkyl group (methyl group, ethyl group, propylgroup, isopropyl group, tert-butyl group and the like), C1-C4 haloalkylgroup (trifluoromethyl group, difluoromethyl group, pentafluoroethylgroup, and the like), C1-C4 alkoxy group (methoxy group, ethoxy group,propxy group, isopropoxy group and the like), C1-C4 alkylthio group(methylthio group, ethylthio group and the like), C1-C2 haloalkoxy group(trifluoromethoxy group, difluoromethoxy group and the like), nitrogroup, cyano group, and halogen atom (fluorine atom, chlorine atom,bromine atom and the like); more specifically, phenyl group,2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group,2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group,4-trifluoromethylphenyl group, 2-methoxyphenyl group, 3-methoxyphenylgroup, 4-methoxyphenyl group, 2-methylthiophenyl group,3-methylthiophenyl group, 4-methylthiophenyl group,2-trifluoromethoxyphenyl group, 3-trifluoromethoxyphenyl group,4-trifluoromethoxyphenyl group, 2-nitrophenyl group, 3-nitrophenylgroup, 4-nitrophenyl group, 2-cyanophenyl group, 3-cyanophenyl group,4-cyanophenyl group, 2-fluorophenyl group, 3-fluorophenyl group,4-fluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenylgroup, 2,6-difluorophenyl group, 2,4-difluorophenyl group,2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group,3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,6-dichlorophenylgroup, 2,4-dichlorophenyl group, 2-bromophenyl group, 3-bromophenylgroup, 4-bromophenyl group, 3,4-dibromophenyl group, 3,5-dibromophenylgroup, 2,6-dibromophenyl group and 2,4-dibromophenyl group.

The C1-C2 alkyl group substituted with a phenyl group, in which thephenyl group may be substituted, represented by R¹ includes, forexample, the C1-C2 alkyl group substituted with a phenyl group in whichthe phenyl group may be substituted with one or more selected from thegroup consisting of C1-C4 alkyl group (methyl group, ethyl group, propylgroup, isopropyl group, tert-butyl group and the like), C1-C4 haloalkylgroup (trifluoromethyl group, difluoromethyl group, pentafluoroethylgroup, and the like), C1-C4 alkoxy group (methoxy group, ethoxy group,propxy group, isopropoxy group and the like), C1-C4 alkylthio group(methylthio group, ethylthio group and the like), C1-C2 haloalkoxy group(trifluoromethoxy group, difluoromethoxy group and the like), nitrogroup, cyano group, and halogen atom (fluorine atom, chlorine atom,bromine atom and the like); more specifically, benzyl group,2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group,2-trifluoromethylbenzyl group, 3-trifluoromethylbenzyl group,4-trifluoromethylbenzyl group, 2-methoxybenzyl group, 3-methoxybenzylgroup, 4-methoxybenzyl group, 2-methylthiobenzyl group,3-methylthiobenzyl group, 4-methylthiobenzyl group,2-trifluoromethoxybenzyl group, 3-trifluoromethoxybenzyl group,4-trifluoromethoxybenzyl group, 2-nitrobenzyl group, 3-nitrobenzylgroup, 4-nitrobenzyl group, 2-cyanobenzyl group, 3-cyanobenzyl group,4-cyanobenzyl group, 2-fluorobenzyl group, 3-fluorobenzyl group,4-fluorobenzyl group, 3,4-difluorobenzyl group, 3,5-difluorobenzylgroup, 2,6-difluorobenzyl group, 2,4-difluorobenzyl group,2-chlorobenzyl group, 3-chlorobenzyl group, 4-chlorobenzyl group,3,4-dichlorobenzyl group, 3,5-dichlorobenzyl group, 2,6-dichlorobenzylgroup, 2,4-dichlorobenzyl group, 2-bromobenzyl group, 3-bromobenzylgroup, 4-bromobenzyl group, 3,4-dibromobenzyl group, 3,5-dibromobenzylgroup, 2,6-dibromobenzyl group, 2,4-dibromobenzyl group, 1-phenylethylgroup, 1-(2-methylphenyl) ethyl group, 1-(3-methylphenyl) ethyl group,1-(4-methylphenyl)ethyl group, 1-(2-trifluoromethylphenyl)ethyl group,1-(3-trifluoromethylphenyl)ethyl group, 1-(4-trifluoromethylphenyl)ethylgroup, 1-(2-methoxyphenyl) ethyl group, 1-(3-methoxyphenyl) ethyl group,1-(4-methoxyphenyl) ethyl group, 1-(2-methylthiophenyl)ethyl group,1-(3-methylthiophenyl)ethyl group, 1-(4-methylthiophenyl)ethyl group,1-(2-trifluoromethoxyphenyl)ethyl group,1-(3-trifluoromethoxyphenyl)ethyl group,1-(4-trifluoromethoxyphenyl)ethyl group, 1-(2-nitrophenyl)ethyl group,1-(3-nitrophenyl)ethyl group, 1-(4-nitrophenyl)ethyl group,1-(2-cyanophenyl)ethyl group, 1-(3-cyanophenyl)ethyl group,1-(4-cyanophenyl)ethyl group, 1-(2-fluorophenyl)ethyl group,1-(3-fluorophenyl)ethyl group, 1-(4-fluorophenyl)ethyl group,1-(3,4-difluorophenyl)ethyl group, 1-(3,5-difluorophenyl)ethyl group,1-(2,6-difluorophenyl)ethyl group, 1-(2,4-difluorophenyl)ethyl group,1-(2-chlorophenyl)ethyl group, 1-(3-chlorophenyl)ethyl group,1-(4-chlorophenyl)ethyl group, 1-(3,4-dichlorophenyl)ethyl group,1-(3,5-dichlorophenyl)ethyl group, 1-(2,6-dichlorophenyl)ethyl group,1-(2,4-dichlorophenyl)ethyl group, 1-(2-bromophenyl)ethyl group,1-(3-bromophenyl)ethyl group, 1-(4-bromophenyl)ethyl group,1-(3,4-dibromophenyl)ethyl group, 1-(3,5-dibromophenyl)ethyl group,1-(2,6-dibromophenyl)ethyl group, 1-(2,4-dibromophenyl)ethyl group,2-phenylethyl group, 2-(2-methylphenyl)ethyl group,2-(3-methylphenyl)ethyl group, 2-(4-methylphenyl)ethyl group,2-(2-trifluoromethylphenyl)ethyl group, 2-(3-trifluoromethylphenyl)ethylgroup, 2-(4-trifluoromethylphenyl)ethyl group, 2-(2-methoxyphenyl)ethylgroup, 2-(3-methoxyphenyl)ethyl group, 2-(4-methoxyphenyl)ethyl group,2-(2-methylthiophenyl)ethyl group, 2-(3-methylthiophenyl)ethyl group,2-(4-methylthiophenyl)ethyl group, 2-(2-trifluoromethoxyphenyl)ethylgroup, 2-(3-trifluoromethoxyphenyl)ethyl group,2-(4-trifluoromethoxyphenyl)ethyl group, 2-(2-nitrophenyl) ethyl group,2-(3-nitrophenyl)ethyl group, 2-(4-nitrophenyl) ethyl group,2-(2-cyanophenyl)ethyl group, 2-(3-cyanophenyl) ethyl group,2-(4-cyanophenyl)ethyl group, 2-(2-fluorophenyl)ethyl group,2-(3-fluorophenyl)ethyl group, 2-(4-fluorophenyl)ethyl group,2-(3,4-difluorophenyl)ethyl group, 2-(3,5-difluorophenyl)ethyl group,2-(2,6-difluorophenyl)ethyl group, 2-(2,4-difluorophenyl)ethyl group,2-(2-chlorophenyl)ethyl group, 2-(3-chlorophenyl)ethyl group,2-(4-chlorophenyl)ethyl group, 2-(3,4-dichlorophenyl)ethyl group,2-(3,5-dichlorophenyl)ethyl group, 2-(2,6-dichlorophenyl)ethyl group,2-(2,4-dichlorophenyl)ethyl group, 2-(2-bromophenyl)ethyl group,2-(3-bromophenyl)ethyl group, 2-(4-bromophenyl)ethyl group,2-(3,4-dibromophenyl)ethyl group, 2-(3,5-dibromophenyl)ethyl group,2-(2,6-dibromophenyl)ethyl and 2-(2,4-dibromophenyl)ethyl group.

The C1-C2 alkyl group substituted with a phenyloxy group, in which thephenyloxy group may be substituted, represented by R¹ includes, forexample, the C1-C2 alkyl group substituted with a phenyloxy group inwhich the phenyloxy group may be substituted with one or more selectedfrom the group consisting of C1-C4 alkyl group (methyl group, ethylgroup, propyl group, isopropyl group, tert-butyl group and the like),C1-C4 haloalkyl group (trifluoromethyl group, difluoromethyl group,pentafluoroethyl group, and the like), C1-C4 alkoxy group (methoxygroup, ethoxy group, propxy group, isopropoxy group and the like), C1-C4alkylthio group (methylthio group, ethylthio group and the like), C1-C2haloalkoxy group (trifluoromethoxy group, difluoromethoxy group and thelike), nitro group, cyano group, and halogen atom (fluorine atom,chlorine atom, bromine atom and the like); more specifically,phenyloxymethyl group, 1-(phenyloxy) ethyl group, 2-(phenyloxy)ethylgroup, (2-methylphenyl)oxymethyl group, (3-methylphenyl)oxymethyl group,(4-methylphenyl)oxymethyl group, (2-trifluoromethylphenyl)oxymethylgroup, (3-trifluoromethylphenyl)oxymethyl group,(4-trifluoromethylphenyl)oxymethyl group, (2-methoxyphenyl)oxymethylgroup, (3-methoxyphenyl)oxymethyl group, (4-methoxyphenyl)oxymethylgroup, (2-methylthiophenyl)oxymethyl group,(3-methylthiophenyl)oxymethyl group, (4-methylthiophenyl)oxymethylgroup, (2-trifluoromethoxyphenyl)oxymethyl group,(3-trifluoromethoxyphenyl)oxymethyl group,(4-trifluoromethoxyphenyl)oxymethyl group, (2-nitrophenyl) oxymethylgroup, (3-nitrophenyl) oxymethyl group, (4-nitrophenyl) oxymethyl group,(2-cyanophenyl) oxymethyl group, (3-cyanophenyl) oxymethyl group,(4-cyanophenyl) oxymethyl group, (2-fluorophenyl)oxymethyl group,(3-fluorophenyl)oxymethyl group, (4-fluorophenyl)oxymethyl group,(3,4-difluorophenyl)oxymethyl group, (3,5-difluorophenyl)oxymethylgroup, (2,6-difluorophenyl)oxymethyl group,(2,4-difluorophenyl)oxymethyl group, (2-chlorophenyl)oxymethyl group,(3-chlorophenyl)oxymethyl group, (4-chlorophenyl)oxymethyl group,(3,4-dichlorophenyl)oxymethyl group, (3,5-dichlorophenyl)oxymethylgroup, (2,6-dichlorophenyl)oxymethyl group,(2,4-dichlorophenyl)oxymethyl group, (2-bromophenyl)oxymethyl group,(3-bromophenyl)oxymethyl group, (4-bromophenyl)oxymethyl group,(3,4-dibromophenyl)oxymethyl group, (3,5-dibromophenyl)oxymethyl group,(2,6-dibromophenyl)oxymethyl group and (2,4-dibromophenyl)oxymethylgroup.

The C2-C3 alkoxyalkyl group substituted with a phenyl group, in whichthe phenyl group may be substituted, represented by R¹ includes, forexample, a methoxymethyl group substituted with a phenyl group in whichthe phenyl group may be substituted with one or more selected from thegroup consisting of C1-C4 alkyl group (methyl group, ethyl group, propylgroup, isopropyl group, tert-butyl group and the like), C1-C4 haloalkylgroup (trifluoromethyl group, difluoromethyl group, pentafluoroethylgroup, and the like), C1-C4 alkoxy group (methoxy group, ethoxy group,propxy group, isopropoxy group and the like), C1-C4 alkylthio group(methylthio group, ethylthio group and the like), C1-C2 haloalkoxy group(trifluoromethoxy group, difluoromethoxy group and the like), nitrogroup, cyano group, and halogen atom (fluorine atom, chlorine atom,bromine atom and the like); more specifically, benzyloxymethyl group,(2-methylbenzyl)oxymethyl group, (3-methylbenzyl)oxymethyl group,(4-methylbenzyl)oxymethyl group, (2-trifluoromethylbenzyl)oxymethylgroup, (3-trifluoromethylbenzyl)oxymethyl group,(4-trifluoromethylbenzyl)oxymethyl group, (2-methoxybenzyl)oxymethylgroup, (3-methoxybenzyl)oxymethyl group, (4-methoxybenzyl)oxymethylgroup, (2-methylthiobenzyl)oxymethyl group,(3-methylthiobenzyl)oxymethyl group, (4-methylthiobenzyl)oxymethylgroup, (2-trifluoromethoxybenzyl)oxymethyl group,(3-trifluoromethoxybenzyl)oxymethyl group,(4-trifluoromethoxybenzyl)oxymethyl group, (2-nitrobenzyl) oxymethylgroup, (3-nitrobenzyl)oxymethyl group, (4-nitrobenzyl)oxymethyl group,(2-cyanobenzyl)oxymethyl group, (3-cyanobenzyl)oxymethyl group,(4-cyanobenzyl)oxymethyl group, (2-fluorobenzyl)oxymethyl group,(3-fluorobenzyl)oxymethyl group, (4-fluorobenzyl)oxymethyl group,(3,4-difluorobenzyl)oxymethyl group, (3,5-difluorobenzyl)oxymethylgroup, (2,6-difluorobenzyl)oxymethyl group,(2,4-difluorobenzyl)oxymethyl group, (2-chlorobenzyl)oxymethyl group,(3-chlorobenzyl)oxymethyl group, (4-chlorobenzyl)oxymethyl group,(3,4-dichlorobenzyl)oxymethyl group, (3,5-dichlorobenzyl)oxymethylgroup, (2,6-dichlorobenzyl)oxymethyl group,(2,4-dichlorobenzyl)oxymethyl group, (2-bromobenzyl)oxymethyl group,(3-bromobenzyl)oxymethyl group, (4-bromobenzyl)oxymethyl group,(3,4-dibromobenzyl)oxymethyl group, (3,5-dibromobenzyl)oxymethyl group,(2,6-dibromobenzyl)oxymethyl group, (2,4-dibromobenzyl) oxymethyl group.

The formula (B) represented by R¹ includes, for example, R³ is a C1-C3alkyl group and R⁴ is a hydrogen atom or a phenyl group in which thephenyl group may be substituted with one or more selected from the groupconsisting of C1-C4 alkyl group (methyl group, ethyl group, propylgroup, isopropyl group, tert-butyl group and the like), C1-C4 haloalkylgroup (trifluoromethyl group, difluoromethyl group, pentafluoroethylgroup, and the like), C1-C4 alkoxy group (methoxy group, ethoxy group,propxy group, isopropoxy group and the like), C1-C4 alkylthio group(methylthio group, ethylthio group and the like), C1-C2 haloalkoxy group(trifluoromethoxy group, difluoromethoxy group and the like), nitrogroup, cyano group, and halogen atom (fluorine atom, chlorine atom,bromine atom and the like); more specifically, acetoxy methyl group andα-acetyloxybenzyl group.

The C1-C4 alkyl group substituted with a hetero ring group (hereinafter,the hetero ring group is referred as the present hetero ring group) inwhich the hetero ring group may be substituted, which the hetero ringgroup is a five-membered ring containing only an oxygen atom(s) or asulfur atom(s) as a hetero atom(s), represented by R² includes, forexample, a C1-C4 alkyl group substituted with the present hetero ringgroup in which the present hetero ring group may be substituted with oneor more selected from the group consisting of C1-C4 alkyl group (methylgroup, ethyl group, propyl group, isopropyl group, tert-butyl group andthe like), halogen atom (fluorine atom, chlorine atom, bromine atom andthe like), trifluoromethyl group, formyl group and nitro group; morespecifically, a methyl group substituted with the present hetero ringgroup in which the present hetero ring group may be substituted with oneor more selected from the group consisting of halogen atom (fluorineatom, chlorine atom, bromine atom and the like), C1-C4 alkyl group(methyl group, ethyl group, propyl group, isopropyl group, tert-butylgroup and the like), trifluoromethyl group, formyl group and nitrogroup, and an ethyl group substituted with the present hetero ring groupat 1-position of ethyl group in which the present hetero ring group maybe substituted with one or more selected from the group consisting ofC1-C4 alkyl group (methyl group, ethyl group, propyl group, isopropylgroup, tert-butyl group and the like), halogen atom (fluorine atom,chlorine atom, bromine atom and the like), trifluoromethyl group, formylgroup and nitro group.

In the C1-C4 alkyl group substituted with the present hetero ring grouprepresented by R², the present hetero ring group includes, for example,a five membered ring group which contains only an oxygen atom(s) as ahetero atom(s), a five membered saturated ring group which contains onlyan oxygen atom(s) as a hetero atom(s), a five membered saturated ringgroup which contains only two oxygen atoms as hetero atoms, a fivemembered ring group which contains only an oxygen atom as a hetero atom,a five membered ring group which contains only a sulfur atom(s) as ahetero atom(s).

The mode of the C1-C4 alkyl group substituted with the present heteroring which the present hetero ring may be substituted represented by R²includes, for example, groups described by the formula (1) to (10) shownbelow.

-   the formula (1):    wherein, in the formula, R¹⁰ represents a hydrogen atom or a methyl    group, R¹¹ represents a halogen atom, a C1-C4 alkyl group, a    trifluoromethyl group, a formyl group, or a nitro group, X¹    represents an oxygen atom or a sulfur atom, m represents 1 or 2, n    represents an integer of 0 to 3. In case of n is an integer of 2 or    more, each of R¹¹s may be same or different; the formula (2):    wherein, in the formula, R¹⁰ represents a hydrogen atom or a methyl    group, R¹² represents a C1-C4 alkyl group, X¹ represents an oxygen    atom or a sulfur atom, m represents 1 or 2, p represents an integer    of 0 to 7. In case of p is an integer of 2 or more, each of R¹²s may    be same or different; the formula (3):    wherein, in the formula, R¹⁰ represents a hydrogen atom or a methyl    group, R¹³ represents a C1-C4 alkyl group, X¹ represents an oxygen    atom or a sulfur atom, m represents 1 or 2, q represents an integer    of 0 to 5. In case of q is an integer of 2 or more, each of R¹³s may    be same or different; the formula (4):    wherein, in the formula, R¹¹ represents a halogen atom, a C1-C4    alkyl group, a trifluoromethyl group, a formyl group or a nitro    group, n represents an integer of 0 to 3. In case of an integer of 2    or more, each of R¹¹s may be same or different; the formula (5):    wherein, in the formula, R¹¹ represents a halogen atom, a C1-C4    alkyl group, a trifluoromethyl group, a formyl group or a nitro    group, n represents an integer of 0 to 3. In case of an integer of 2    or more, each of R¹¹s may be same or different; the formula (6):    wherein, in the formula, R¹² represents a C1-C4 alkyl group, p    represents an integer of 0 to 7. In case of p is an integer of 2 or    more, each of R¹²s may be same or different; the formula (7):    wherein, in the formula, R¹² represents a C1-C4 alkyl group, p    represents an integer of 0 to 7. In case of p is an integer of 2 or    more, each of R¹²s may be same or different; the formula (8):    wherein, in the formula, R¹³ represents a C1-C4 alkyl group, q    represents an integer of 0 to 5. In case of q is an integer of 2 or    more, each of R¹³s may be same or different; the formula (9):    wherein, in the formula, R¹³ represents a C1-C4 alkyl group, q    represents an integer of 0 to 5. In case of q is an integer of 2 or    more, each of R¹³s may be same or different; the formula (10):    wherein, in the formula, R¹³ represents a C1-C4 alkyl group, two    R¹³'s are the same or different from each other.

Embodiments of the compound of the present invention include, forexample, the following compounds:

-   the thiadiazole compound wherein R¹ is a C1-C7 alkyl group in the    formula (A);-   the thiadiazole compound wherein R¹ is a C3-C7 alkenyl group, a    C2-C7 alkoxyalkyl group, a C2-C7 alkylthioalkyl group, C4-C7    alkoxyalkoxyalkyl group or C4-C7 alkylthioalkoxyalkyl group in the    formula (A);-   the thiadiazole compound wherein R¹ is a phenyl group in which the    phenyl group may be substituted with one or more selected from the    Substituent Group A, a C1-C2 alkyl group substituted with a phenyl    group in which the phenyl group may be substituted with one or more    selected from the Substituent Group A, a C1-C2 alkyl group    substituted with a phenyloxy group in which the phenyloxy group may    be substituted with one or more selected from the Substituent Group    A or a C2-C3 alkoxyalkyl group substituted with a phenyl group in    which the phenyl group may be substituted with one or more selected    from the Substituent Group A,    -   Substituent Group A    -   C1-C4 alkyl group, C1-C4 haloalkyl group, C1-C4 alkoxy group,        C1-C4 alkylthio group, C1-C4 haloalkoxy group, nitro group,        cyano group, and halogen atoms, in the formula (A);-   the thiadiazole compound wherein R¹ is a group designated by formula    (B):    wherein, in the formula, R³ represents a C1-C3 alkyl group, R⁴    represents a hydrogen atom, a methyl group, an ethyl group, or a    phenyl group optionally substituted with one or more selected from    C1-C4 alkyl group, C1-C4 haloalkyl group, C1-C4 alkoxy group, C1-C4    alkylthio group, C1-C4 haloalkoxy group, nitro group, cyano group    and halogen atoms,-   in the formula (A);-   the thiadiazole compound wherein R¹ is a phenyl group optionally    substituted with one or more selected from the Substituent Group A,    a benzyl group optionally substituted with one or more selected from    the Substituent Group A, phenyloxymethyl group optionally    substituted with one or more selected from the Substituent Group A    or benzyloxymethyl group optionally substituted with one or more    selected from the Substituent Group A in the formula (A); the    thiadiazole compound wherein R² is a group designated by the formula    (1):    wherein, in the formula, R¹⁰ represents a hydrogen atom or a methyl    group, R¹¹ represents a halogen atom, a C1-C4 alkyl group, a    trifluoromethyl group, a formyl group or a nitro group, X¹    represents an oxygen atom or a sulfur atom, m represents 1 or 2, n    represents an integer of 0 to 3, in case of n is an integer of 2 or    more, each of R¹¹s may be same or different, a group designated by    the formula (2):    wherein, in the formula, R¹⁰ represents a hydrogen atom or a methyl    group, R¹² represents a C1-C4 alkyl group, X¹ represents an oxygen    atom or a sulfur atom, m represents 1 or 2, p represents an integer    of 0 to 7, in case of p is an integer of 2 or more, each of R¹²s may    be same or different, or a group designated by the formula (3):    wherein, in the formula, R¹⁰ represents a hydrogen atom or a methyl    group, R¹³ represents a C1-C4 alkyl group, X¹ represents an oxygen    atom or a sulfur atom, m represents 1 or 2, q represents an integer    of 0 to 5, in case of q is an integer of 2 or more, each of R¹³s may    be same or different-   in the formula (A);-   the thiadiazole compound wherein R¹ is a group designated by the    formula (4):    wherein, in the formula, R¹¹ represents a halogen atom, a C1-C4    alkyl group, a trifluoromethyl group, a formyl group and a nitro    group, n represents an integer of 0 to 3, in case of n is an integer    of 2 or more, each of R¹¹s may be same or different, a group    designated by the formula (5):    wherein, in the formula, R¹¹ represents a halogen atom, a C1-C4    alkyl group, a trifluoromethyl group, a formyl group and a nitro    group, n represents an integer of 0 to 3, in case of n is an integer    of 2 or more, each of R¹¹s may be same or different, a group    designated by the formula (6):    wherein, in the formula, R¹² represents a C1-C4 alkyl group, p    represents an integer of 0 to 7, in case of p is an integer of 2 or    more, each of R¹²s may be same or different, a group designated by    the formula (7):    wherein, in the formula, R¹² represents a C1-C4 alkyl group, p    represents an integer of 0 to 7, in case of p is an integer of 2 or    more, each of R¹²s may be same or different,-   a group designated by the formula (8):    wherein, in the formula, R¹³ represents a C1-C4 alkyl group, q    represents an integer of 0 to 5, in case of q is an integer of 2 or    more, each of R¹³s may be same or different, a group designated by    the formula (9):    wherein, in the formula, R¹³ represents a C1-C4 alkyl group, q    represents an integer of 0 to 5, in case of q is an integer of 2 or    more, each of R¹³s may be same or different, or a group designated    by the formula (10):    wherein, in the formula, R¹³ represents a C1-C4 alkyl group, two    R¹³s are the same or different from each other.

The following will describe a production process for the compound of thepresent invention.

In the compound of the present invention, the compound wherein R¹represents a C1-C7 alkyl group, a C3-C7 alkenyl group, a C3-C7 alkynylgroup, a C2-C7 alkoxyalkyl group, a C2-C7 alkylthioalkyl group, a C4-C7alkoxyalkoxyalkyl group, a C4-C7 alkylthioalkoxyalkyl group, a phenylgroup in which the phenyl group may be substituted, a phenyl C1-C2 alkylgroup in which the phenyl may be substituted, a phenyloxy C1-C2 alkylgroup in which the phenyloxy may be substituted or a phenyl C2-C3alkoxyalkyl group in which the phenyl may be substituted, namely thecompound shown by the formula (A-1), can be produced, for example, bymaking a 5-chloro-1,2,4-tiadiazole compound shown by the formula (I)react with an alcohol compound shown by the formula (II).

wherein, in the formula, R¹⁻¹ represents a C1-C7 alkyl group, a C3-C7alkenyl group, a C3-C7 alkynyl group, a C2-C7 alkoxyalkyl group, a C2-C7alkylthioalkyl group, a C4-C7 alkoxyalkoxyalkyl group, a C4-C7alkylthioalkoxyalkyl group, a phenyl group in which the phenyl group maybe substituted, a phenyl C1-C2 alkyl group in which the phenyl may besubstituted, a phenyloxy C1-C2 alkyl group in which the phenyloxy may besubstituted or a phenyl C2-C3 alkoxyalkyl group in which the phenyl maybe substituted; R² has a same meaning as described above.

The reaction is usually carried out in the presence of a base, usuallyin a solvent.

The solvent to be used to the reaction includes, for example, aliphatichydrocarbons such as hexane, heptane, octane and the like; aromatichydrocarbons such as toluene, xylene and the like; ethers such astetrahydrofuran, 1,4-dioxane, methyl-tert-butylether, 1,2-dimethoyethaneand the like; N,N-dimethylformamide, and the mixture thereof.

The base to be used to the reaction includes, for example, carbonatessuch as potassium carbonate, sodium carbonate and the like, and themixture thereof.

Concerning to the amount of the reagent to be used to the reaction, theamount of the alcohol compound shown by the formula (II) is usually 1 to1.5 moles relative to 1 mole of the 5-chloro-1,2,4-tiadiazole compoundshown by the formula (I), the amount of the base is 1 to 1.5 molesrelative to the alcohol compound shown by the formula (II).

The reaction temperature is usually in the range of −20 to 80° C., andthe reaction time is usually in the range of 0.5 to 24 hours.

After completion of the reaction, the compound of the present inventionshown by the formula (A-1) can be islated by subjecting the reactionmixture to post-treatment such as adding the reaction mixture intowater, extracting with anorganic solvent, drying and consentrating theextract and the like. The islated compound of the present inventionshown by the formula (A-1) can be purified by a techniqe such aschromatography, recrystallization and the like, if necessary.

In the compound of the present invention, the compound wherein R¹represents the group shown by the formula (B), namely the compound shownby the formula (A-2), can be produced by, for example, by making thethiadiazole compound shown by the formula (III) react with oxidizingagent (hereinafter, referred as the first half step), after that, makingthe product of the first half step react with acid anhydride shown bythe formula (V) (hereinafter, referred as the later half step).

whrein, in the formula, R², R³ and R⁴ have same meanings as describedabove.(The First Half Step)

The reaction of the first half step is usually carried out in a solvent.The solvent to be used to the reaction includes, for example,halogenated aliphatic hydrocarbons such as dichloromethane, chloroformand the like and water.

The oxidizing agent to be used to the reaction includes, for example,peroxy acids such as 3-chloroperoxybenzoic acid. The amount of theoxidizing agent to be used to the reaction is usually 1 to 1.5 molesrelative to 1 mole of the thiadiazole compound shown by the formula(III).

The reaction temperature is usually in the range of −20 to 30° C., andthe reaction time is usually in the range of momentary to 24 hours.

After completion of the reaction, the sulfoxide compound shown by theformula (IV) can be islated by subjecting the reaction mixture topost-treatment such as adding the reaction mixture into water;extracting with an organic solvent; if necessary washing the obtainedorganic layer with an aquous solution of reductant such as sodiumsulfite, sodium thiosulfate and the like, an aquous solution of base(sodium bicarbonate and the like); drying and consentrating the organiclayer and the like. The islated the sulfoxide compound shown by theformula (IV) can be purified by a techniqe such as chromatography,recrystallization and the like.

(The Later Half Step)

The later half step can be carried out by making the slufoxide compoundshown by the formula (IV) react with the acid anhydride shown by theformula (V).

The reaction is carried out in the presence of a solvent or absence of asolvent, and usually in the presence of a base.

The base to be used to the reaction inclueds, for example, pyridinessuch as 2,6-lutidine and the like, alkali metal salts of acetic acidsuch as sodium acetate and the like.

Concerning to the amount of the reagent to be used to the reaction, theamount of the acid anhydride shown by the formula (V) is 1 to 50 molesrelative to 1 mole of the sulfoxide compound shown by the formula (IV),the amount of the base is 1 to 10 moles relative to the sulfoxidecompound shown by the formula (IV).

The reaction can be carried out in the presence of trifluoroaceticanhydride, if necessary. In this case, the amount of trifluoroaceticanhydride is usually 0.01 to 5 moles relative to 1 mole of the sulfoxidecompound shown by the formula (IV).

The reaction temperature is usually in the range of 0 to 150° C., andthe reaction time is usually in the range of 1 to 72 hours.

After completion of the reaction, the compound of the present inventionshown by the formula (A-2) can be islated by subjecting the reactionmixture to post-treatment such as adding the reaction mixture intoaquous solution of a base (ex. sodiumbicarbonate), extracting with anorganic solvent, drying and consentrating the obtained organic layer andthe like. The islated compound of the present invention shown by theformula (A-2) can be purified by a techniqe such as chromatography,recrystallization and the like, if necessary.

The compound shown by the formula (I) can be produced, for example, bythe method described in Chem. Ber. 90, 892(1957).

Next, examples of the present compounds are shown.

In the formula (i) to the formula (xx), R¹ represents one of the groupselected from methyl group, ethyl group, propyl group, isopropyl group,butyl group, sec-butyl group, tert-butyl group, allyl group, 2-butenylgroup, 3-methyl-2-butenyl group, 2-pentenyl group, 2-propynyl group,1-methyl-2-propynyl group, 2-butynyl group, 3-butynyl group, 2-pentynylgroup, methoxymethyl group, ethoxymethyl group, propoxymethyl group,isopropoxymethyl group, butoxymethyl group, isobutoxymethyl group,sec-butoxymethyl group, tert-butoxymethyl group, methylthiomethyl group,ethylthiomethyl group, propylthiomethyl group, isopropylthiomethylgroup, methoxyethoxymethyl group, ethoxyethoxymethyl group,methylthioethoxymethyl group, phenyl group, 2-methylphenyl group,3-methylphenyl group, 4-methylphenyl group, 2-trifluoromethylphenylgroup, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group,2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group,2-methylthiophenyl group, 3-methylthiophenyl group, 4-methylthiophenylgroup, 2-trifluoromethoxyphenyl group, 3-trifluoromethoxyphenyl group,4-trifluoromethoxyphenyl group, 2-nitrophenyl group, 3-nitrophenylgroup, 4-nitrophenyl group, 2-cyanophenyl group, 3-cyanophenyl group,4-cyanophenyl group, 2-fluorophenyl group, 3-fluorolphenyl group,4-fluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorolphenylgroup, 2,6-difluorophenyl group, 2,4-difluorophenyl group,2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group,3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,6-dichlorophenylgroup, 2,4-dichlorophenyl group, 2-bromophenyl group, 3-bromophenylgroup, 4-bromophenyl group, 3,4-dibromophenyl group, 3,5-dibromophenylgroup, 2,6-dibromophenyl group, 2,4-dibromophenyl group, benzyl group,2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group,2-trifluoromethylbenzyl group, 3-trifluoromethylbenzyl group,4-trifluoromethylbenzyl group, 2-methoxybenzyl group, 3-methoxybenzylgroup, 4-methoxybenzyl group, 2-methythiobenzyl group,3-methylthiobenzyl group, 4-methylthiobenzyl group,2-trifluoromethoxybenzyl group, 3-trifluoromethoxybenzyl group,4-trifluoromethoxybenzyl group, 2-nitrobenzyl group, 3-nitrobenzylgroup, 4-nitrobenzyl group, 2-cyanobenzyl group, 3-cyanobenzyl group,4-cyanobenzyl group, 2-flourobenzyl group, 3-flourobenzyl group,4-flourobenzyl group, 3,4-diflourobenzyl group, 3,5-diflourobenzylgroup, 2,6-diflourobenzyl group, 2,4-diflourobenzyl group,2-chlorobenzyl group, 3-chlorobenzyl group, 4-chlorobenzyl group,3,4-dichlorobenzyl group, 3,5-dichlorobenzyl group, 2,6-dichlorobenzylgroup, 2,4-dichlorobenzyl group, 2-bromobenzyl group, 3-bromobenzylgroup, 4-bromobenzyl group, 3,4-dibromobenzyl group, 3,5-dibromobenzylgroup, 2,6-dibromobenzyl group, 2,4-dibromobenzyl group, 1-(phenyl)ethylgroup, 1-(2-methylphenyl)ethyl group, 1-(3-methylphenyl)ethyl group,1-(4-methylphenyl)ethyl group, 1-(2-trifluoromethylphenyl)ethyl group,1-(3-trifluoromethylphenyl)ethyl group, 1-(4-trifluoromethylphenyl)ethylgroup, 1-(2-methoxyphenyl)ethyl group, 1-(3-methoxyphenyl) ethyl group,1-(4-methoxyphenyl)ethyl group, 1-(2-methylthiophenyl)ethyl group,1-(3-methylthiophenyl)ethyl group, 1-(4-methylthiophenyl)ethyl group,1-(2-trifluoromethoxyphenyl)ethyl group,1-(3-trifluoromethoxyphenyl)ethyl group,1-(4-trifluoromethoxyphenyl)ethyl group, 1-(2-nitrophenyl)ethyl group,1-(3-nitrophenyl)ethyl group, 1-(4-nitrophenyl)ethyl group,1-(2-cyanophenyl)ethyl group, 1-(3-cyanophenyl)ethyl group,1-(4-cyanophenyl)ethyl group, 1-(2-fluorophenyl)ethyl group,1-(3-fluorophenyl)ethyl group, 1-(4-fluorophenyl)ethyl group,1-(3,4-difluorophenyl)ethyl group, 1-(3,5-difluorophenyl)ethyl group,1-(2,6-difluorophenyl)ethyl group, 1-(2,4-difluorophenyl)ethyl group,1-(2-chlorophenyl)ethyl group, 1-(3-chlorophenyl)ethyl group,1-(4-chlorophenyl)ethyl group, 1-(3,4-dichlorophenyl)ethyl group,1-(3,5-dichlorophenyl)ethyl group, 1-(2,6-dichlorophenyl)ethyl group,1-(2,4-dichlorophenyl)ethyl group, 1-(2-bromophenyl)ethyl group,1-(3-bromophenyl) ethyl group, 1-(4-bromophenyl)ethyl group,1-(3,4-dibromophenyl) ethyl group, 1-(3,5-dibromophenyl) ethyl group,1-(2,6-dibromophenyl) ethyl group, 1-(2,4-dibromophenyl)ethyl group,2-(phenyl)ethyl group, 2-(2-methylphenyl)ethyl group,2-(3-methylphenyl)ethyl group, 2-(4-methylphenyl)ethyl group,2-(2-trifluoromethylphenyl)ethyl group, 2-(3-trifluoromethylphenyl)ethylgroup, 2-(4-trifluoromethylphenyl)ethyl group, 2-(2-methoxyphenyl) ethylgroup, 2-(3-methoxyphenyl) ethyl group, 2-(4-methoxyphenyl)ethyl group,2-(2-methylthiophenyl)ethyl group, 2-(3-methylthiophenyl)ethyl group,2-(4-methylthiophenyl)ethyl group, 2-(2-trifluoromethoxyphenyl)ethylgroup, 2-(3-trifluoromethoxyphenyl)ethyl group,2-(4-trifluoromethoxyphenyl)ethyl group, 2-(2-nitrophenyl)ethyl group,2-(3-nitrophenyl)ethyl group, 2-(4-nitrophenyl)ethyl group,2-(2-cyanophenyl)ethyl group, 2-(3-cyanophenyl)ethyl group,2-(4-cyanophenyl)ethyl group, 2-(2-fluorophenyl)ethyl group,2-(3-fluorophenyl)ethyl group, 2-(4-fluorophenyl)ethyl group,2-(3,4-difluorophenyl)ethyl group, 2-(3,5-difluorophenyl)ethyl group,2-(2,6-difluorophenyl)ethyl group, 2-(2,4-difluorophenyl)ethyl group,2-(2-chlorophenyl)ethyl group, 2-(3-chlorophenyl)ethyl group,2-(4-chlorophenyl)ethyl group, 2-(3,4-dichlorophenyl)ethyl group,2-(3,5-dichlorophenyl)ethyl group, 2-(2,6-dichlorophenyl)ethyl group,2-(2,4-dichlorophenyl)ethyl group, 2-(2-bromophenyl)ethyl group,2-(3-bromophenyl)ethyl group, 2-(4-bromophenyl)ethyl group,2-(3,4-dibromophenyl) ethyl group, 2-(3,5-dibromophenyl)ethyl group,2-(2,6-dibromophenyl)ethyl group, 2-(2,4-dibromophenyl)ethyl group,phenyloxymethyl group, 1-(phenyloxy)ethyl group, 2-(phenyloxy)ethylgroup, (2-methylphenyl)oxymethyl group, (3-methylphenyl)oxymethyl group,(4-methylphenyl)oxymethyl group, (2-trifluoromethylphenyl)oxymethylgroup, (3-trifluoromethylphenyl)oxymethyl group,(4-trifluoromethylphenyl)oxymethyl group, (2-methoxyphenyl)oxymethylgroup, (3-methoxphenyl)oxymethyl group, (4-methoxphenyl)oxymethyl group,(2-methythiophenyl)oxymethyl group, (3-methylthiophenyl)oxymethyl group,(4-methylthiophenyl)oxymethyl group, (2-trifluoromethoxyphenyl)oxymethylgroup, (3-trifluoromethoxphenyl)oxymethyl group,(4-trifluoromethoxphenyl)oxymethyl group, (2-nitrophenyl)oxymethylgroup, (3-nitrophenyl) oxymethyl group, (4-nitrophenyl)oxymethyl group,(2-cyanophenyl)oxymethyl group, (3-cyanophenyl) oxymethyl group,(4-cyanophenyl)oxymethyl group, (2-fluorophenyl)oxymethyl group,(3-fluorophenyl)oxymethyl group, (4-fluorophenyl)oxymethyl group,(3,4-difluorophenyl)oxymethyl group, (3,5-difluorophenyl)oxymethylgroup, (2,6-difluorophenyl)oxymethyl group,(2,4-difluorophenyl)oxymethyl group, (2-cholorophenyl)oxymethyl group,(3-cholorophenyl) oxymethyl group, (4-cholorophenyl)oxymethyl group,(3,4-dicholorophenyl)oxymethyl group, (3,5-dicholorophenyl)oxymethylgroup, (2,6-dicholorophenyl)oxymethyl group,(2,4-dicholorophenyl)oxymethyl group, (2-bromophenyl)oxymethyl group,(3-bromophenyl) oxymethyl group, (4-bromophenyl)oxymethyl group,(3,4-dibromophenyl)oxymethyl group, (3,5-dibromophenyl)oxymethyl group,(2,6-dibromophenyl)oxymethyl group, (2,4-dibromophenyl)oxymethyl group,benzyloxymethyl group, (2-methylbenzyl)oxymethyl group,(3-methylbenzyl)oxymethyl group, (4-methylbenzyl)oxymethyl group,(2-trifluoromethylbenzyl)oxymethyl group,(3-trifluormethylbenzyl)oxymethyl group,(4-trifluormethylbenzyl)oxymethyl group, (2-methoxybenzyl) oxymethylgroup, (3-methoxybenzyl) oxymethyl group, (4-methoxybenzyl)oxymethylgroup, (2-methylthiobenzyl)oxymethyl group,(3-methylthiobenzyl)oxymethyl group, (4-methylthiobenzyl)oxymethylgroup, (2-trifluoromethoxybenzyl)oxymethyl group,(3-trifluoromethoxybenzyl)oxymethyl group,(4-trifluoromethoxybenzyl)oxymethyl group, (2-nitrobenzyl)oxymethylgroup, (3-nitrobenzyl) oxymethyl group, (4-nitrobenzyl)oxymethyl group,(2-cyanobenzyl) oxymethyl group, (3-cyanobenzyl) oxymethyl group,(4-cyanobenzyl)oxymethyl group, (2-fluorobenzyl)oxymethyl group,(3-fluorobenzyl)oxymethyl group, (4-fluorobenzyl)oxymethyl group,(3,4-difluorobenzyl)oxymethyl group, (3,5-difluorobenzyl)oxymethylgroup, (2,6-difluorobenzyl)oxymethyl group,(2,4-difluorobenzyl)oxymethyl group, (2-chlorobenzyl)oxymethyl group,(3-chlorobenzyl)oxymethyl group, (4-chlorobenzyl)oxymethyl group,(3,4-dichlorobenzyl)oxymethyl group, (3,5-dichlorobenzyl)oxymethylgroup, (2,6-dichlorobenzyl)oxymethyl group,(2,4-dichlorobenzyl)oxymethyl group, (2-bromobenzyl)oxymethyl group,(3-bromobenzyl) oxymethyl group, (4-bromobenzyl)oxymethyl group,(3,4-dibromobenzyl)oxymethyl group, (3,5-dibromobenzyl)oxymethyl group,(2,6-dibromobenzyl)oxymethyl group, (2,4-dibromobenzyl)oxymethyl group,acetyloxymethyl group, propioniloxymethyl group and α-acetoxybenzylgroup.

The arthropod pests against which the compound of the present inventionhas control activity may include insect pests and acarine pests.Specific examples are listed below.

-   -   Hemiptera: Delphacidae such as Laodelphax striatellus,        Nilaparvata lugens, and Sogatella furcifera; Deltocephalidae        such as Nephotettix cincticeps and Empoasca onukii; Aphididae        such as Aphis gossypii and Myzus persicae; Pentatomidae;        Aleyrodidae such as Trialeurodes vaporariorum, Bemisia tabaci,        and Bemisia argentifolii; Coccidae; Tingidae; Psyllidae;    -   Lepidoptera: Pyralidae such as Chilo suppressalis,        Cnaphalocrocis medinalis, Ostrinia nubilalis, and Parapediasia        teterrella; Noctuidae such as Spodoptera litura, Spodoptera        exigua, Pseudaletia separata, Mamestra brassicae, Agrotis        ipsilon, Thoricoplusia spp., Heliothis spp., Helicoverpa spp.,        and Earias spp.; Pieridae such as Pieris rapae crucivora;        Tortricidae such as Adoxophyes orana fasciata, Grapholita        molesta, and Cydia pomonella; Carposinidae such as Carposina        niponensis; Lyonetiidae such as Lyonetia clerkella;        Gracillariidae such as Phyllonorycter ringoniella;        Phyllocnistidae such as Phyllocnistis citrella; Yponomeutidae        such as Plutela xylostella; Gelechiidae such as Pectinophora        gossypiella; Arctiidae; Tineidae;    -   Diptera: Calicidae such as Culex pipiens pallens, Culex        tritaeniorhynchus, and Culex quinquefasciatus; Aedes spp. such        as Aedes aegypti and Aedes albopictus; Anopheles spp. such as        Anopheles sinensis; Chironomidae; Muscidae such as Musca        domestica and Muscina stabulans; Calliphoridae; Sarcophagidae;        Fanniidae; Anthomyiidae such as Delia platura and Delia antiqua;        Tephritidae; Drosophilidae; Psychodidae; Tabanidae; Simuliidae;        Stomoxyidae; Agromyzidae;    -   Coleoptera: Diabrotica spp. such as Diabrotica virgifera        virgifera and Diabrotica undecimpunctata howardi; Scarabaeidae        such as Anomala cuprea and Anomala rufocuprea; Curculionidae        such as Sitophilus zeamais, Lissorhoptrus oryzophilus, and        Callosobruchuys chienensis; Tenebrionidae such as Tenebrio        molitor and Tribolium castaneum; Chrysomelidae such as Oulema        oryzae, Aulacophora femoralis, Phyllotreta striolata, and        Leptinotarsa decemlineata; Anobiidae; Epilachna spp. such as        Epilachna vigintioctopunctata; Lyctidae; Bostrychidae;        Cerambycidae; Paederus fuscipes;    -   Thysanoptera: Thripidae spp. including Thrips spp. such as        Thrips palmi, Frankliniella spp. such as Frankliniella        occidentalis, and Sciltothrips spp. such as Sciltothrips        dorsalis; Phlaeothripidae spp.;    -   Hymenoptera: Tenthredimidae; Formicidae; Vespidae;    -   Dictyoptera: Periplaneta spp.; Blatta spp.;    -   Orthoptera: Acrididae; Gryllotalpidae;    -   Aphaniptera: Pulex irritans;    -   Anoplura: Pediculus humanus;    -   Isoptera: Termitidae;    -   Acarina: Tetranychidae.

The arthropod pests comtrolling composition of the present inventioncomprises the compound of the present invention and an inert carrier.

Generally, it is a formulation obtained by mixing the compound of thepresent invention, and a solid carrier, a liquid carrier, a gaseouscarrier and/or bait (base material for poision bait) and the like, ifnecessary, adding a surfactant and other adjuvant for formulation. Theformulation includes, for example, an oils lution, an emulsifiableconcentrate, a flowable, a wettable powder, a granule, a dust, amicrocapsule and the like. These formulation can converted to use into apoison bait or a sheet. It is the arthropod pests controllingcomposition of the present invention. The arthropod pests controllingcomposition of the present invention is usually contained in an amountof 0.01 to 95% by weight of the compound of the present invention.

The solid carrier for formulation includes, for example, a fine powerand a granule of clays (kaolin clay, diatomite, bentonite, Fubasamiclay, acid clay, etc.), synthetic hydrated siliconoxide, talc, ceramic,other inorganic minerals (sericite, quartz, sulfur, activated carbon,calcium carbonate, etc.) or chemical fertilizers (ammonium sulfate,ammonium nitrate, ammonium chloride, etc.). The liquid carrier includes,for example, water, alcohols (methanol, ethanol, 2-propanol, ethyleneglycol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutylketone, cyclohexanone, etc.), aromatic hydrocarbons (toluene, xylene,ethylbenzen, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane,cyclohexane, kerosine, light oil, etc.), esters (ethyl acetate, butylacetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers(ethylene glycol dimethyl ether, diisopropyl ether, 1,4-dioxane,tetrahydrofuran, etc.), acid amides (N,N-dimethylformamide,N,N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane,trichloroethane, etc.), dimethylsulfoxide and vegetable oils (soy beanoil, cotton seed oil, etc.).

The gaseous carrier includes, for example, fluorocarbons, butane gas,LPG (liquefied petroleum gas), dimethyl ether and carbon dioxide.

The surfactant includes, for example, alkyl sulfate salts, alkylsulfonicacid salts, alkylarylsulfonic acid salts, alkyl aryl ethers and theirpolyoxyethylene derivatives, polyethylene glycol ethers, polyhydricalcohol esters, and sugar alcohol derivatives.

The other adjuvant for formulation includes, for example, stickingagents, dispersing agents and stabilizing agents, and specifically forexample, casein, gelatin, polysaccharides (starch, gum arabic, cellulosederivatives, alginic acid, etc.), lignin derivatives, syntheticwater-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone,polyacrylic acid, etc.), PAP (isopropyl acid phosphate), BHT(2,6-di-t-butyl-4-methylphenol), BHA (a mixture of2-t-butyl-4-methoxyphenol and 3-t-butyl-4-methoxyphenol), mineral oils,fatty acids, and fatty acid esters.

A base material for the poison bait includes, for example, baitingredients such as grain powders, vegetable oils, sugars, andcrystalline cellulose. The poison bait may be added, if necessary,antioxidants such as dibutylhydroxytoluene and nordihydroguaiareticacid, preservatives such as dehydroacetic acid, agents for preventingfrom erroneously eating such as hot pepper powder, and pest-attractiveflavors such as cheese flavor, onion flavor and peanut oil.

The arthropod pests controlling composition of the present invention isused by applying the arthropod pests controlling composition to pestsdirectly and/or habitats of pests (nest, plant, soil, etc.). In the caseof controlling the arthropod pest which is parasitic on a cultivatingplant, for example, the arthropod pests controlling composition of thepresent invention is sprayed onto the upper side of the cultivatingplant, pouring into the vicinities of a root of the cultivation plantand the like.

When the arthropod pests controlling composition of the presentinvention is used for a control of arthropod pests in agriculture andforestry, the application amount is usually 0.1 to 10,000 g as thecompound of the present invention per 1,000 m². In case of the arthropodpests controlling composition of the present invention are formulated toemulsifiable concentrates, flowables, wettable powders andmicrocapsules, they are usually applied by spraying after dilution withwater to have the concentration of the compound of the present inventionto 10 to 10,000 ppm. In case of the arthropod pests controllingcomposition of the present invention are formulated to oil solutions,dusts and granules, they are usually applied as such.

When the arthropod pests controlling composition of the presentinvention is used for a control of epidemic, the application amount isusually 0.001 to 100 mg as the compound of the present invention per 1 m2 in case of application for plane surface, and 0.001 to 10 mg as thecompound of the present invention per 1 m³ in case of application foropen space. In the case of the arthropod pests controlling compositionof the present invention are formulated to emulsifiable concentrates,flowables, wettable powders and microcapsules, they are usually appliedafter dilution with water to have the concentration of the compound ofthe present invention to 0.01 to 100,000 ppm. In case of the arthropodpests controlling composition of the present invention are formulated tooil solutions, aerosols, smoking agents and poison baits are usuallyapplied as such.

The arthropod pests controlling composition of the present invention canalso be used with other insecticides, nematocides, acaricides,fungicides, herbicides, plant growth regulators, synergists,fertilizers, soil conditioners, animal feeds, and the like.

Such insecticides and acaricides include, for example, organophosphoruscompounds such as fenitrothion, fenthion, pyridaphenthion, diazinon,chlorpyrifos, chlorpyrifos-methyl, acephate, methidathion, disulfoton,DDVP, sulprofos, profenofos, cyanophos, dioxabenzofos, dimethoate,phenthoate, malathion, trichlorfon, azinphos-methyl, monocrotophos,dicrotophos, ethion, and fosthiazate; carbamate compounds such as BPMC,benfuracarb, propoxur, carbosulfan, carbaryl, methomyl, ethiofencarb,aldicarb, oxamyl, fenothiocarb, and thiodicarb; pyrethroid compoundssuch as etofenprox, fenvalerate, esfenvalerate, fenpropathrin,cypermethrin, alfa-cypermethrin, zeta-cypermethrin, permethrin,cyhalothrin, lambda-cyhalothrin, cyfluthrin, beta-cyfluthrin,deltamethrin, cycloprothrin, tau-fluvalinate, flucythrinate, bifenthrin,acrinathrin, tralomethrin, silafluofen, and halfenprox; neonicotinoidcompounds such as acetamiprid, thiamethoxam, and thiacloprid;benzoylphenylurea compounds such as chlorfluazuron, teflubenzuron,flufenoxuron, and lufenuron; benzoylhydrazide compounds such astebufenozide, halofenozide, methoxyfenozide and chromafenozide;thiadiazine derivatives such as buprofezin; nereistoxin derivatives suchas cartap, thiocyclam, and bensultap; chlorinated hydrocarbon compoundssuch as endosulfan, gamma-BHC, and1,1-bis(chlorophenyl)-2,2,2-trichloroethanol; formamidine derivativessuch as amitraz and chlordimeform; thiourea derivatives such asdiafenthiuron; phenylpyrazole derivatives such as ethiprole, andacetoprole; chlorfenapyr; pymetrozine; spinosad; indoxacarb;bromopropylate; tetradifon; chinomethionat; propargite; fenbutatinoxide; hexythiazox; etoxazole; clofentezine; pyridaben; pyridalyl;fenpyroximate; tebufenpyrad; pyrimidifen; fenazaquin; acequinocyl;bifenazate; fluacrypyrim; spirodiclofen; spiromesifen; milbemectin;avermectin; emamectin benzoate; azadirachtin; polynactin complexes suchas tetranactin, idinactin, and trinactin; and the like.

The present invention will be further illustrated by the followingproduction examples, formulation examples and test examples and thelike; however, the present invention is not limited to these examples.In the following production examples, the data of ¹H-NMR were measuredin a solvent of deuterium chloroform with tetramethylsilane as theinternal standard.

Production examples of the compound of the present invention areexemplified.

PRODUCTION EXAMPLE 1

To 2 g of N,N-dimethylformamide, 0.257 g of5-chloro-3-(4-methylbenzyl)thio-1,2,4-thiadiazole and 0.145 g of2,2-dimethyl-1,3-dioxolane-4-methanol were dissolved, and added 48 mg ofsodium hydride (60% in oil) at about 0° C., followed by stirring atabout 0° C. for 30 minutes and at room temperature for 4 hours. Then,the reaction mixture was added to saturated sodium chloride aqueoussolution, and extracted with tert-butylmethylether. The organic layerwas concentrated, and the residue obtaind was subjected to silica gelcolumn chromatography to obtain 0.27 g of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(4-methylbenzyl)thio-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(4-methylbenzyl)thio-1,2,4-thiadiazole(Which is Reffered to as the Compound of the Present Invention 1Hereinafter)

¹H-NMR:7.29 (d, 2H) 7.11 (d, 2H) 4.54-4.44 (m, 3H) 4.37 (d, 2H)4.15-4.11 (m, 1H) 3.83-3.80 (m, 1H) 2.32 (s, 3H) 1.45 (s, 3H) 1.38 (s,3H)

PRODUCTION EXAMPLE 2

To 2 g of N,N-dimethylformamide, 312 mg of crude product of5-chloro-3-(3,4-dichlorobenzyl)thio-1,2,4-thiadiazole which was producedby Reference Production Example 8 desbribed below and 0.145 g of2,2-dimethyl-1,3-dioxolane-4-methanol were dissolved, and added 48 mg ofsodium hydride (60% in oil) at about 0° C., followed by stirring atabout 0° C. for 30 minutes and at room temperature for 4 hours. Then,the reaction mixture was added to saturated sodium chloride aqueoussolution, and extracted with tert-butylmethylether. The organic layerwas concentrated, and the residue obtaind was subjected to silica gelcolumn chromatography to obtain 120 mg of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(3,4-dichlorobenzyl)thio-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(3,4-dichlorobenzyl)thio-1,2,4-thiadiazole(Which is Reffered to as the Compound of the Present Invention 2Hereinafter)

¹H-NMR:7.55 (s, 1H) 7.36 (d, 1H) 7.26-7.22 (m, 1H) 4.55-4.44 (m, 3H)4.31 (s, 2H) 4.15-4.09 (m, 1H) 3.84-3.80 (m, 1H) 1.45 (s, 3H) 1.38 (s,3H)

PRODUCTION EXAMPLE 3

To 40 ml of N,N-dimethylformamide, 3.34 g of5-chloro-3-methylthio-1,2,4-thiadiazole which was produced by ReferenceProduction Example 1 desbribed below and 2.90 g of2,2-dimethyl-1,3-dioxolane-4-methanol were dissolved, and added 880 mgof sodium hydride (60% in oil) at about 0° C., followed by stirring atsame temperature for 1 hour. Then, the reaction mixture was added tosaturated sodium chloride aqueous solution, and extracted withtert-butylmethylether. The organic layer was dried by anhydrous sodiumsulfate, and the concentrated residue obtaind was subjected to silicagel column chromatography to obtain 4.67 g of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-methylthio-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-methylthio-1,2,4-thiadiazole(Which is Reffered to as the Compound of the Present Invention 3Hereinafter)

¹H-NMR:4.57-4.46 (m, 3H) 4.16-4.09 (m, 1H) 3.85-3.81 (m, 1H) 2.60 (s,3H) 1.45 (s, 3H) 1.35 (s, 3H)

PRODUCTION EXAMPLE 4

To 2 ml of N,N-dimethylformamide, 300 mg of crude product of5-chloro-3-(3-chlorobenzyl)thio-1,2,4-thiadiazole which was produced byReference Production Example 6 desbribed below and 157 mg of2,2-dimethyl-1,3-dioxolane-4-methanol were dissolved, and added 52 mg ofsodium hydride (60% in oil), followed by stirring at room temperaturefor 2 hours. Then, the reaction mixture was added to saturated sodiumchloride aqueous solution, and extracted with tert-butylmethylether. Theorganic layer was dried by anhydrous sodium sulfate, and theconcentrated residue obtaind was subjected to silica gel columnchromatography to obtain 150 mg of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(3-chlorobenzyl)thio-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(3-chlorobenzyl)thio-1,2,4-thiadiazole(Which is Reffered to as the Compound of the Present Invention 4Hereinafter)

¹H-NMR:7.42 (s, 1H) 7.31-7.22 (m, 2H) 4.54-4.45 (m, 3H) 4.35 (s, 2H)4.16-4.11 (m, 1H) 3.85-3.81 (m, 1H) 1.45 (s, 3H) 1.38 (s, 3H)

PRODUCTION EXAMPLE 5

To 2 ml of N,N-dimethylformamide, 300 mg of crude product of5-chloro-3-(2-chlorobenzyl) thio-1,2,4-thiadiazole which was produced byReference Production Example 5 desbribed below and 157 mg of2,2-dimethyl-1,3-dioxolane-4-methanol were dissolved, and added 52 mg ofsodium hydride (60% in oil), followed by stirring at room temperaturefor 2 hours. Then, the reaction mixture was added to saturated sodiumchloride aqueous solution, and extracted with tert-butylmethylether. Theorganic layer was dried by anhydrous sodium sulfate, and theconcentrated residue obtaind was subjected to silica gel columnchromatography to obtain 140 mg of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(2-chlorobenzyl)thio-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(2-chlorobenzyl)thio-1,2,4-thiadiazole(Which is Reffered to as the Compound of the Present Invention 5Hereinafter)

¹H-NMR:7.56 (m, 1H) 7.37 (m, 1H) 7.20 (m, 2H) 4.56-4.45 (m, 5H)4.15-4.11 (m, 1H) 3.84-3.80 (m, 1H) 1.45 (s, 3H) 1.38 (s, 3H)

PRODUCTION EXAMPLE 6

To 2 ml of N,N-dimethylformamide, 200 mg of5-chloro-3-(4-methoxybenzyl)thio-1,2,4-thiadiazole which was produced byReference Production Example 4 desbribed below and 153 mg of2,2-dimethyl-1,3-dioxolane-4-methanol were dissolved, and added 35 mg ofsodium hydride (60% in oil) at about 0° C., followed by stirring atabout 0° C. for 15 minutes and at room temperature for 2 hours. Then,the reaction mixture was added to saturated sodium chloride aqueoussolution, and extracted with tert-butylmethylether. The organic layerwas dried by anhydrous sodium sulfate, and the concentrated residueobtaind was subjected to silica gel column chromatography to obtain 200mg of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(4-methoxybenzyl)thio-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(4-methoxybenzyl)thio-1,2,4-thiadiazole(Which is Reffered to as the Compound of the Present Invention 6Hereinafter)

¹H-NMR:7.33 (d, 2H) 6.84 (d, 2H) 4.54-4.46 (m, 3H) 4.36 (s, 2H)4.15-4.13 (m, 1H) 3.84-3.79 (m, 4H) 1.45 (s, 3H) 1.38 (s, 3H)

PRODUCTION EXAMPLE 7

To 3 ml of N,N-dimethylformamide, 416 mg of crude product of5-chloro-3-(4-chlorobenzyl)thio-1,2,4-thiadiazole which was produced byReference Production Example 3 desbribed below and 198 mg of2,2-dimethyl-1,3-dioxolane-4-methanol were dissolved, and added 72 mg ofsodium hydride (60% in oil) at about 0° C., followed by stirring at sametemperature for about 1 hour. Then, the reaction mixture was added tosaturated sodium chloride aqueous solution, and extracted withtert-butylmethylether. The organic layer was dried by anhydrous sodiumsulfate, and the concentrated residue obtaind was subjected to silicagel column chromatography to obtain 460 mg of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(4-chlorobenzyl)thio-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(4-chlorobenzyl)thio-1,2,4-thiadiazole(Which is Reffered to as the Compound of the Present Invention 7Hereinafter)

¹H-NMR:7.36 (d, 2H) 7.27 (d, 2H) 4.55-4.44 (m, 2H) 4.35 (s, 2H)4.17-4.10 (m, 1H) 3.84-3.81 (s, 1H) 1.47 (s, 3H) 1.38 (s, 3H)

PRODUCTION EXAMPLE 8

To 5 ml of N,N-dimethylformamide, 340 mg of5-chloro-3-benzylthio-1,2,4-thiadiazole which was produced by ReferenceProduction Example 2 desbribed below and 222 mg of2,2-dimethyl-1,3-dioxolane-4-methanol were dissolved, and added 84 mg ofsodium hydride (60% in oil) at about 0° C., followed by stirring at roomtemperature for about 1 hour. Then, the reaction mixture was added tosaturated sodium chloride aqueous solution, and extracted withtert-butylmethylether. The organic layer was dried by anhydrous sodiumsulfate, and the concentrated residue obtaind was subjected to silicagel column chromatography to obtain 370 mg of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-benzylthio-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-benzylthio-1,2,4-thiadiazole(Which is Reffered to as the Compound of the Present Invention 8Hereinafter)

¹H-NMR:7.42 (d, 2H) 7.34-7.24 (m, 3H) 4.55-4.43 (m, 3H) 4.40 (s, 2H)4.15-4.12 (m, 1H) 3.84-3.81 (m, 1H) 1.45 (s, 3H) 1.35 (s, 3H)

PRODUCTION EXAMPLE 9

To 4 g of N,N-dimethylformamide, 386 mg of5-chloro-3-allylthio-1,2,4-thiadiazole which was produced by ReferenceProduction Example 10 desbribed below and 277 mg of2,2-dimethyl-1,3-dioxolane-4-methanol were dissolved, and added 88 mg ofsodium hydride (60% in oil) under ice cooling. After the mixture wasstirred under ice cooling for 1 hour, the reaction mixture was added tosaturated sodium chloride aqueous solution, and extracted withtert-butylmethylether. The organic layer was dried by anhydrous sodiumsulfate, and the concentrated residue obtaind was subjected to silicagel column chromatography to obtain 530 mg of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-allylthio-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-allylthio-1,2,4-thiadiazole(Which is Reffered to as the Compound of the Present Invention 9Hereinafter)

¹H-NMR:5.96 (m, 1H) 5.32 (d, 1H) 5.15 (d, 1H) 4.51 (m, 3H) 4.13 (m, 1H)3.84 (m, 3H) 1.45 (s, 3H) 1.36 (s, 3H)

PRODUCTION EXAMPLE 10

To 4 ml of N,N-dimethylformamide, 362 mg of5-chloro-3-ethylthio-1,2,4-thiadiazole which was produced by ReferenceProduction Example 7 desbribed below and 264 mg of2,2-dimethyl-1,3-dioxolane-4-methanol were dissolved, and added 88 mg ofsodium hydride (60% in oil) at about 0° C., followed by stirring at sametemperature for 30 minutes. Then, the reaction mixture was added tosaturated sodium chloride aqueous solution, and extracted withtert-butylmethylether. The organic layer was dried by anhydrous sodiumsulfate, and the concentrated residue obtaind was subjected to silicagel column chromatography to obtain 410 mg of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-ethylthio-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-ethylthio-1,2,4-thiadiazole(Which is Reffered to as the Compound of the Present Invention 10Hereinafter)

¹H-NMR:4.51 (m, 3H) 4.14 (m, 1H) 3.84 (m, 1H) 3.17 (q, 2H) 1.41 (m, 9H)

PRODUCTION EXAMPLE 11

To 2 g of N,N-dimethylformamide, 0.243 g of5-chloro-3-benzylthio-1,2,4-thiadiazole and 0.098 g of 3-furanmethanolwere dissolved, and added 0.045 g of sodium hydride (60% in oil) atabout 0° C., followed by stirring at about 0° C. for 1 hour and at roomtemperature for 2 hours. Then, the reaction mixture was added tosaturated sodium chloride aqueous solution, and extracted withtert-butylmethylether. The organic layer was concentrated, and theresidue obtaind was subjected to silica gel column chromatography toobtain 0.17 g of 5-(3-furyl)methoxy-3-benzylthio-1,2,4-thiadiazole.

5-(3-furyl)methoxy-3-benzylthio-1,2,4-thiadiazole (Which is Reffered toas the Compound of the Present Invention 11 Hereinafter)

¹H-NMR:7.56 (s, 1H) 7.42 (m, 3H) 7.30 (m, 3H) 6.50 (s, 1H) 5.37 (s, 2H)4.41 (s, 2H)

PRODUCTION EXAMPLE 12

To 4 ml of N,N-dimethylformamide, 0.334 g of5-chloro-3-methylthio-1,2,4-thiadiazole and 0.196 g of 2-furanmethanolwere dissolved, and added 0.084 g of sodium hydride (60% in oil) atabout 0° C., followed by stirring at about 0° C. for 0.5 hours and atroom temperature for 4 hours. Then, the reaction mixture was added tosaturated sodium chloride aqueous solution, and extracted withtert-butylmethylether. The organic layer was concentrated, and theresidue obtaind was subjected to silica gel column chromatography toobtain 0.25 g of 5-(2-furyl)methoxy-3-methylthio-1,2,4-thiadiazole.

5-(2-furyl)methoxy-3-methylthio-1,2,4-thiadiazole (Which is Reffered toas the Compound of the Present Invention 12 Hereinafter)

¹H-NMR:7.47 (m, 1H) 6.56 (m, 1H) 6.40 (m, 1H) 5.45 (s, 2H) 2.62 (s, 3H)

PRODUCTION EXAMPLE 13

By using 0.196 g of 3-furanmethanol instead of 2-furanmethanol accordingto Production Example 12 was obtained 390 mg of5-(3-furyl)methoxy-3-methylthio-1,2,4-thiadiazole.5-(3-furyl)methoxy-3-methylthio-1,2,4-thiadiazole (which is reffered toas the compound of the present invention 13 hereinafter)

¹H-NMR:7.58 (s, 1H) 7.43 (d, 1H) 6.51 (d, 1H) 5.38 (s, 2H) 2.62 (s, 3H)

PRODUCTION EXAMPLE 14

By using 204 mg of tetrahydro-3-furaemethanol instead of 2-furanmethanolaccording to Production Example 12 was obtained 406 mg of5-(tetrahydro-3-furyl)methoxy-3-methylthio-1,2,4-thiadiazole.

5-(tetrahydro-3-furyl)methoxy-3-methylthio-1,2,4-thiadiazole (Which isReffered to as the Compound of the Present Invention 14 Hereinafter)

¹H-NMR:4.49-4.36 (m, 2H) 3.93-3.65 (m, 4H) 2.84-2.74 (m, 1H) 2.60 (s,3H) 2.17-2.05 (m, 1H) 1.76-1.65 (m, 1H)

PRODUCTION EXAMPLE 15

To 10 ml of N,N-dimethylformamide, 835 mg of3-methylthio-5-chloro-1,2,4-thiadiazole and 520 mg of glycerol formalwere dissolved, and added 204 mg of sodium hydride (60% in oil) at about0° C., followed by stirring at about 0° C. for 20 minutes and at roomtemperature for 30 minutes. Then, the reaction mixture was added tosaturated sodium chloride aqueous solution, and extracted withtert-butylmethylether. After the organic layer was dried by anhyroussodium salfate, the organic layer was concentrated, and the residueobtaind was subjected to silica gel column chromatography (hexane:ethylacetate=20:1), followed preparative HPLC to obtain 250 mg of5-(1,3-dioxolane-4-yl)methoxy-3-methylthio-1,2,4-thiadiazole.

5-(1,3-dioxolane-4-yl)methoxy-3-methylthio-1,2,4-thiadiazole (Which isReffered to as the Compound of the Present Invention 15 Hereinafter)

¹H-NMR:5.08 (s, 1H) 4.93 (s, 1H) 4.55-4.45 (m, 3H) 4.06-4.02 (m, 1H)3.82-3.78 (m, 1H) 2.60 (s, 3H)

PRODUCTION EXAMPLE 16

To 4 ml of N,N-dimethylformamide, 0.334 g of5-chloro-3-methylthio-1,2,4-thiadiazole and 228 mg of2-thiophenemethanol were dissolved, and added 0.084 g of sodium hydride(60% in oil) at about 0° C., followed by stirring at about 0° C. for 0.5hours and at room temperature for 4 hours. Then, the reaction mixturewas added to saturated sodium chloride aqueous solution, and extractedwith tert-butylmethylether. The organic layer was concentrated, and theresidue obtaind was subjected to silica gel column chromatography toobtain 66 mg of 5-(2-thienyl)methoxy-3-methylthio-1,2,4-thiadiazole.

5-(2-thienyl)methoxy-3-methylthio-1,2,4-thiadiazole (Which is Refferedto as the Compound of the Present Invention 16 Hereinafter)

¹H-NMR:7.38 (d, 1H) 7.25 (d, 1H) 7.22 (m, 1H) 5.65 (s, 2H) 2.62 (s, 3H)

PRODUCTION EXAMPLE 17

To 4 ml of N,N-dimethylformamide, 0.334 g of5-chloro-3-methylthio-1,2,4-thiadiazole and 228 mg of3-thiophenemethanol were dissolved, and added 0.084 g of sodium hydride(60% in oil) at about 0° C., followed by stirring at about 0° C. for 0.5hours and at room temperature for 4 hours. Then, the reaction mixturewas added to saturated sodium chloride aqueous solution, and extractedwith tert-butylmethylether. The organic layer was concentrated, and theresidue obtaind was subjected to silica gel column chromatography toobtain 500 mg of 5-(3-thienyl)methoxy-3-methylthio-1,2,4-thiadiazole.

5-(3-thienyl)methoxy-3-methylthio-1,2,4-thiadiazole (Which is Refferedto as the Compound of the Present Invention 17 Hereinafter)

¹H-NMR:7.43 (m, 1H) 7.35 (m, 1H) 7.17 (m, 1H) 5.49 (s, 2H) 2.61 (s, 3H)

PRODUCTION EXAMPLE 18

(1) To 90 ml of chloroform, 4.67 g of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-methylthio-1,2,4-thiadiazolewas dissolved, and added 3.92 g of 3-chloroperoxybenzoic acid (purity70%) which was devided to small portions at about 0° C., followed bystirring. Then, the reaction mixture was added to saturated sodiumsulfite aqueous solution, and extracted with chloroform. The organiclayer was successively washed with saturated sodium bicarbonate aqueoussolution, saturated sodium chloride aqueous solution, dried by anhyroussodium salfate, and concentrated. The residue was subjected to silicagel column chromatography to obtain 3.87 g of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-methaneslufinyl-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-methaneslufinyl-1,2,4-thiadiazole

¹H-NMR:4.67-4.49 (m, 3H) 4.18-4.14 (m, 1H) 3.86-3.32 (m, 1H) 2.30 (s,3H) 1.46 (s, 3H) 1.39 (s, 3H)

(2) 2.97 g of 2,6-lutidine, 11.3 g of acetic anhydride and 4.38 g oftrifluoroacetic anhydride were added to 3.87 g of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-methaneslufinyl1,2,4-thiadiazole and mixed at about 0° C., followed by standing at roomtemperature for 3 days. Then, after the reaction mixture wasconcentrated under reduced pressure. The residue was added to saturatedsodium bicarbonate aqueous solution, and extracted withtert-butylmethylether. The organic layer was concentrated, and theresidue obtaind was subjected to silica gel column chromatography toobtain 0.18 g of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(acetyloxymethyl)thio-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(acetyloxymethyl)thio-1,2,4-thiadiazole(Which is Reffered to as the Compound of the Present Invention 18Hereinafter)

¹H-NMR:5.75 (s, 2H) 4.57-4.47 (m, 3H) 4.17-4.13 (m, 1H) 3.85-3.82 (m,1H) 2.11 (s, 3H) 1.45 (s, 3H) 1.39 (s, 3H)

PRODUCTION EXAMPLE 19

(1) To 4 ml of chloroform, 370 mg of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-benzylthio-1,2,4-thiadiazolewas dissolved, and added 269 mg of 3-chloroperoxybenzoic acid (purity70%) which was devided to small portions under ice cooling, followed bystirring. Then, the reaction mixture was added to saturated sodiumsulfite aqueous solution, and extracted with chloroform. The organiclayer was successively washed with saturated sodium bicarbonate aqueoussolution, saturated sodium chloride aqueous solution, dried by anhyroussodium salfate, and concentrated. The residue was subjected to silicagel column chromatography to obtain 360 mg of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-phenylslufinyl-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-phenylslufinyl-1,2,4-thiadiazole

¹H-NMR:7.33-7.19 (m, 5H) 4.66-4.48 (m, 3H) 4.42 (d, 1H) 4.34 (d, 1H)4.18-4.14 (m, 1H) 3.86-3.82 (m, 1H) 1.47 (s, 3H) 1.40 (s, 3H)

(2) To 80 g of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-phenylslufinyl-1,2,4-thiadiazole,100 mg of sodium acetate and 2 ml of acetic anhydride were added andmixed at 0° C., followed by refluxing for 14 hours. Then, the reactionmixture was added to saturated sodium bicarbonate aqueous solution, andextracted with tert-butylmethylether. The organic layer wasconcentrated, and the residue obtaind was subjected to silica gel columnchromatography to obtain 28 mg of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(α-acetyloxybenzyl)thio-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(α-acetyloxybenzyl)thio-1,2,4-thiadiazole(Which is Reffered to as the Compound of the Present Invention 19Hereinafter)

¹H-NMR:7.74-7.73 (m, 1H) 7.53-7.51 (m, 2H) 7.41-7.35 (m, 3H) 4.58-4.32(m, 3H) 4.20-4.07 (m, 1H) 3.86-3.73 (m, 1H) 2.10 (s, 3H) 1.46 (s, 3H)1.39 (s, 3H)

PRODUCTION EXAMPLE 20

To 3 g of N,N-dimethylformamide, 468 mg of crude product of5-chloro-3-(3,5-dichlorobenzyl)thio-1,2,4-thiadiazole which was producedby Reference Production Example 11 desbribed below and 198 mg of2,2-dimethyl-1,3-dioxolane-4-methanol were dissolved, and added 42 mg ofsodium hydride (60% in oil) at about 0° C., followed by stirring for 30minutes. Then, to the reaction mixture, t-butylmethylether and saturatedsodium chloride aqueous solution were added, and separeted to twolayers. The organic layer was dried by anhydrous sodium salfate, andconcentrated. The residue obtaind was subjected to column chromatographyto obtain 72 mg of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(3,5-dichlorobenzyl)thio-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(3,5-dichlorobenzyl)thio-1,2,4-thiadiazole(Which is Reffered to as the Compound of the Present Invention 20Hereinafter)

¹H-NMR:7.32 (s, 2H) 7.24 (s, 1H) 4.54-4.43 (m, 3H) 4.30 (s, 2H)4.15-4.11 (m, 1H) 3.84-3.81 (m, 1H) 1.48 (s, 3H) 1.41 (s, 3H)

PRODUCTION EXAMPLE 21

To 2 g of N,N-dimethylformamide, 300 mg of5-chloro-3-(3-trifluoromethylbenzyl)thio-1,2,4-thiadiazole which wasproduced by Reference Production Example 12 desbribed below and 127 mgof 2,2-dimethyl-1,3-dioxolane-4-methanol were dissolved, and added 42 mgof sodium hydride (60% in oil) at about 0° C., followed by stirring atabout 0° C. for 30 minutes and at room tempareture for 2 hours. Then, tothe reaction mixture, t-butylmethylether and saturated sodium chlorideaqueous solution were added, and separeted to two layers. The organiclayer was dried by anhydrous sodium salfate, and concentrated. Theresidue obtaind was subjected to column chromatography to obtain 370 mgof5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(3-trifluoromethylbenzyl)thio-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-(3-trifluoromethylbenzyl)thio-1,2,4-thiadiazole(Which is Reffered to as the Compound of the Present Invention 21Hereinafter)

¹H-NMR:7.69 (s, 1H)7.61 (d, 1H)7.50 (d, 1H)7.42 (t, 1H)4.55-4.42 (m,5H)4.15-4.11 (m, 1H)3.84-3.81 (m, 1H)1.45 (s, 3H)1.38 (s, 3H)

PRODUCTION EXAMPLE 22

To 3 g of N,N-dimethylformamide, 300 mg of5-chloro-3-ethoxymethylthio-1,2,4-thiadiazole and 188 mg of2,2-dimethyl-1,3-dioxolane-4-methanol were dissolved, and added 62 mg ofsodium hydride (60% in oil) at about 0° C., followed by stirring atabout 0° C. for 30 minutes and standing at room tempareture for about 1day. Then, to the reaction mixture, t-butylmethylether and saturatedsodium chloride aqueous solution were added, and separeted to twolayers. The organic layer was dried by anhydrous sodium salfate, andconcentrated. The residue obtaind was subjected to column chromatographyto obtain 330 mg of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-ethoxymethylthio-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-ethoxymethylthio-1,2,4-thiadiazole(Which is Reffered to as the Compound of the Present Invention 22Hereinafter)

¹H-NMR:5.39 (s, 2H) 4.58-4.47 (m, 3H) 4.16-4.11 (m, 1H) 3.86-3.82 (m,1H) 3.68-3.63 (q, 2H) 1.45 (s, 3H) 1.39 (s, 3H) 1.23 (t, 3H)

PRODUCTION EXAMPLE 23

To 3 g of N,N-dimethylformamide, 350 mg of5-chloro-3-benzyloxymethylthio-1,2,4-thiadiazole and 169 mg of2,2-dimethyl-1,3-dioxolane-4-methanol were dissolved, and added 56 mg ofsodium hydride (60% in oil) at about 0° C., followed by stirring at sametempareture for 2 hours. Then, to the reaction mixture,t-butylmethylether and saturated sodium chloride aqueous solution wereadded, and separeted to two layers. The organic layer was dried byanhydrous sodium salfate, and concentrated. The residue obtaind wassubjected to column chromatography to obtain 330 mg of5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-benzyloxymethylthio-1,2,4-thiadiazole.

5-(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy-3-benzyloxymethylthio-1,2,4-thiadiazole(Which is Reffered to as the Compound of the Present Invention 23Hereinafter)

¹H-NMR:7.36-7.28 (m, 5H) 5.41 (s, 2H) 4.69 (s, 2H) 4.57-4.46 (m, 3H)4.16-4.11 (m, 1H) 3.85-3.82 (m, 1H) 1.45 (s, 3H) 1.39 (s, 3H)

Next, the production of the 5-chloro-1,2,4-thiadiazole compound which isthe intermediate of the compound of the present invention is describedas Reference Production Examples.

REFERENCE PRODUCTION EXAMPLE 1

To 100 ml of water, 18.7 g of methylisothiourea sulfate, 25 g ofperchloromethylmercaptan, 0.15 g of sodiumdodecyl sulfate were added,followed the solution of 21 g of sodium hydroxide dissolved to 100 ml ofwater was added dropwise over a period for about 4 hours at about 0° C.After completion of addition, the mixture was stirred at sametempareture for 2 hours. Then, t-butylmethylether was added to thereaction mixture, and extracted. The organic layer was concentrated. Theresidue obtaind was distilled under reduced pressure, followed bysubjecting to silica gel column chromatography (hexane:ethylacetate=25:1) to obtain 7.64 g of3-methylthio-5-chloro-1,2,4-thiadiazole.

3-methylthio-5-chloro-1,2,4-thiadiazole

¹H-NMR:2.66 (s, 3H)

REFERENCE PRODUCTION EXAMPLE 2

To the mixture of 20 ml of toluene and 10 ml of water, 2.02 g ofbenzylisothiourea hydrochloride, 1.86 g of perchloromethylmercaptan and46 mg of benzyltriethylammonium chloride were added, followed thesolution of 1.6 g of sodium hydroxide dissolved to 10 ml of water wasadded dropwise at about 0° C., and then stirred for 2 hours. Then,t-butylmethylether was added to the reaction mixture, and extracted. Theorganic layer was dried by anhydrous sodium salfate, and concentratedThe residue obtaind was subjected to silica gel column chromatography(hexane:ethylacetate=20:1) to obtain 900 mg of3-benzylthio-5-chloro-1,2,4-thiadiazole.

3-benzylthio-5-chloro-1,2,4-thiadiazole

¹H-NMR:7.60-7.20 (m, 5H)4.45 (s, 2H)

REFERENCE PRODUCTION EXAMPLE 3

To the mixture of 80 ml of toluene and 40 ml of water, 10.0 g of4-chlorobenzylisothiourea hydrochloride, 7.85 g ofperchloromethylmercaptan and 192 mg of benzyltriethylammonium chloridewere added, followed the solution of 6.75 g of sodium hydroxidedissolved to 40 ml of water was added dropwise over a period for 3 hoursat about 0° C. Then, t-butylmethylether was added to the reactionmixture, and extracted. The organic layer was dried by anhydrous sodiumsalfate, and concentrated. The residue obtaind was subjected to silicagel column chromatography to obtain 5.38 g of3-(4-chlorobenzyl)thio-5-chloro-1,2,4-thiadiazole.

3-(4-chlorobenzyl)thio-5-chloro-1,2,4-thiadiazole

¹H-NMR:7.37 (d, 2H)7.27 (d, 2H)4.40 (s, 2H)

REFERENCE PRODUCTION EXAMPLE 4

To the mixture of 20 ml of toluene and 10 ml of water, 2.53 g of4-methoxybenzylisothiourea hydrochloride, 2.03 g ofperchloromethylmercaptan and 50 mg of benzyltriethylammonium chloridewere added, followed the solution of 1.74 g of sodium hydroxidedissolved to 10 ml of water was added dropwise over a period for 4 hoursat about 0° C. After completion of addition, the mixture was stirred atroom tempareture for 1 hour. Then, t-butylmethylether was added to thereaction mixture, and extracted. The organic layer was dried byanhydrous sodium salfate. The concentrated residue obtaind was subjectedto silica gel column chromatography to obtain 5.38 g of3-(4-methoxybenzyl)thio-5-chloro-1,2,4-thiadiazole.

3-(4-methoxybenzyl)thio-5-chloro-1,2,4-thiadiazole

¹H-NMR:7.35 (d, 2H)6.85 (d, 2H)4.41 (s, 2H)3.79 (s, 3H)

REFERENCE PRODUCTION EXAMPLE 5

To the mixture of 80 ml of toluene and 40 ml of water, 10.0 g of2-chlorobenzylisothiourea hydrochloride, 7.85 g ofperchloromethylmercaptan and 192 mg of benzyltriethylammonium chloridewere added, followed the solution of 5.27 g of sodium hydroxidedissolved to 40 ml of water was added dropwise over a period for 1 hourat about 0° C. Then, t-butylmethylether was added to the reactionmixture, and extracted. The organic layer was dried by anhydrous sodiumsalfate, and concentrated. The residue obtaind was subjected to silicagel column chromatography to obtain 0.78 g of3-(2-chlorobenzyl)thio-5-chloro-1,2,4-thiadiazole.

3-(2-chlorobenzyl)thio-5-chloro-1,2,4-thiadiazole

¹H-NMR:7.55 (d, 1H)7.49 (d, 1H)7.22 (m, 2H)4.57 (s, 2H)

REFERENCE PRODUCTION EXAMPLE 6

To the mixture of 80 ml of toluene and 40 ml of water, 10.0 g of3-chlorobenzylisothiourea hydrochloride, 7.85 g ofperchloromethylmercaptan and 192 mg of benzyltriethylammonium chloridewere added, followed the solution of 5.27 g of sodium hydroxidedissolved to 40 ml of water was added dropwise over a period for 1 hourat about 0° C. Then, t-butylmethylether was added to the reactionmixture, and extracted. The organic layer was dried by anhydrous sodiumsalfate, and concentrated. The residue obtaind was subjected to silicagel column chromatography to obtain 1.30 g of3-(3-chlorobenzyl)thio-5-chloro-1,2,4-thiadiazole.

3-(3-chlorobenzyl)thio-5-chloro-1,2,4-thiadiazole

¹H-NMR:7.43 (s, 1H)7.31-7.22 (m, 3H)4.41 (s, 2H)

REFERENCE PRODUCTION EXAMPLE 7

To 60 ml of water, 10.3 g of ehtylisothiourea hydrobromide, 10.4 g ofperchloromethylmercaptan were added, followed the solution of 9.39 g ofsodium hydroxide dissolved to 60 ml of water was added dropwise slowlyat about 0° C. Then, t-butylmethylether was added to the reactionmixture, and extracted. The organic layer was dried by anhydrous sodiumsalfate, and concentrated. The residue obtaind was subjected to silicagel column chromatography (hexanne:ethylacetate=30:1) to obtain 2.54 gof 3-ethylthio-5-chloro-1,2,4-thiadiazole.

3-ethylthio-5-chloro-1,2,4-thiadiazole

¹H-NMR:3.22 (q, 2H)1.44 (t, 3H)

REFERENCE PRODUCTION EXAMPLE 8

To 50 ml of water, 12.9 g of 3,4-dichlorobenzylisothiourea hydrochlorideand 8.82 g of perchloromethylmercaptan were added, followed the solutionof 7.58 g of sodium hydroxide dissolved to 50 ml of water was addeddropwise slowly at about 0° C., followed by stirring for 4 hours. Then,t-butylmethylether was added to the reaction mixture, and extracted. Theorganic layer was dried by anhydrous sodium salfate, and concentrated.The residue obtaind was subjected to silica gel column chromatography toobtain 3.1 g of 3-(3,4-dichlorobenzyl)thio-5-chloro-1,2,4-thiadiazole asa crude product.

3-(3,4-dichlorobenzyl)thio-5-chloro-1,2,4-thiadiazole

REFERENCE PRODUCTION EXAMPLE 9

To 50 ml of water, 9.46 g of 4-methylbenzylisothiourea hydrochloride and8.11 g of perchloromethylmercaptan were added, followed the solution of6.98 g of sodium hydroxide dissolved to 50 ml of water was addeddropwise at about 0° C., followed by stirring for 4 hours. Then,t-butylmethylether was added to the reaction mixture, and extracted. Theorganic layer was dried by anhydrous sodium salfate, and concentrated.The residue obtaind was subjected to silica gel column chromatography toobtain 3.6 g of 3-(4-methylbenzyl)thio-5-chloro-1,2,4-thiadiazole as acrude product.

3-(4-methylbenzyl)thio-5-chloro-1,2,4-thiadiazole

REFERENCE PRODUCTION EXAMPLE 10

To 50 ml of water, 9.33 g of allylisothiourea hydrochloride and 8.82 gof perchloromethylmercaptan were added, followed the solution of 7.58 gof sodium hydroxide dissolved to 50 ml of water was added dropwise atabout 0° C., followed by stirring for 4 hours. Then, t-butylmethyletherwas added to the reaction mixture, and extracted. The organic layer wasdried by anhydrous sodium salfate, and concentrated. The residue obtaindwas subjected to silica gel column chromatography to obtain 3.6 g of3-allylthio-5-chloro-1,2,4-thiadiazole.

3-allylthio-5-chloro-1,2,4-thiadiazole

¹H-NMR:6.03-5.83 (m, 1H)5.34 (d, 1H)5.19 (d, 1H)3.88 (d, 1H)

REFERENCE PRODUCTION EXAMPLE 11

To the mixture of 25 ml of water and 25 ml of dichloromethane, 8.95 g of3,5-dichlorobenzylisothiourea hydrochloride and 6.12 g ofperchloromethylmercaptan were added, followed the solution of 5.26 g ofsodium hydroxide dissolved to 50 ml of water was added dropwise at about0° C. over the period for about 3 hours. After completion of addition,the mixture was stirred at room tempareture for 1 hour. Then, chloroformwas added to the reaction mixture, and extracted. The organic layer wasdried by anhydrous sodium salfate, and concentrated. The residue obtaindwas subjected to silica gel column chromatography(hexane:ethylacetate=30:1) to obtain 2.4 g of crude3-(3,5-dichlorobenzyl)thio-5-chloro-1,2,4-thiadiazole as a crudeproduct.

REFERENCE PRODUCTION EXAMPLE 12

To the mixture of 25 ml of water and 50 ml of dichloromethane, 12.0 g of3-trifluoromethylbenzylisothiourea hydrochloride and 8.24 g ofperchloromethylmercaptan were added, followed the solution of 7.09 g ofsodium hydroxide dissolved to 25 ml of water was added dropwise at about0° C. over the period for about 1.5 hours. After completion of addition,the mixture was stirred at room tempareture for 2 hours. Then,chloroform was added to the reaction mixture, and extracted. The organiclayer was dried by anhydrous sodium salfate, and concentrated. Theresidue obtaind was subjected to silica gel column chromatography(hexane:ethylacetate=20:1) to obtain 5.9 g of3-(3-trifluoromethylbenzyl)thio-5-chloro-1,2,4-thiadiazole.3-(3-trifluoromethylbenzyl)-5-chloro-1,2,4-thiadiazole

¹H-NMR:7.69 (s, 1H)7.61 (d, 1H)7.52 (d, 1H)7.44 (t, 1H)4.47 (s, 2H)

REFERENCE PRODUCTION EXAMPLE 13

To the mixture of 35 ml of water and 70 ml of dichloromethane, 12.2 g ofethoxymethylisothiourea hydrochloride and 13.2 g ofperchloromethylmercaptan were added, followed the solution of 11.4 g ofsodium hydroxide dissolved to 35 ml of water was added dropwise at about0° C. over the period for about 1.5 hours. After completion of addition,the mixture was stirred at room tempareture for 1 hour. Then, chloroformwas added to the reaction mixture, and extracted. The organic layer wasdried by anhydrous sodium salfate, and concentrated. The residue obtaindwas subjected to silica gel column chromatography to obtain 5.22 g of3-ethoxymethylthio-5-chloro-1,2,4-thiadiazole.

3-ethoxymethylthio-5-chloro-1,2,4-thiadiazole

¹H-NMR:5.43 (s, 2H)3.68 (q, 2H)1.26 (t, 3H)

REFERENCE PRODUCTION EXAMPLE 14

To the mixture of 25 ml of water and 50 ml of dichloromethane, 11.3 g ofbenzyloxymethylisothiourea hydrochloride and 9.02 g ofperchloromethylmercaptan were added, followed the solution of 7.76 g ofsodium hydroxide dissolved to 25 ml of water was added dropwise at about0° C. over the period for about 1.5 hours. After completion of addition,the mixture was stirred at room tempareture for 1 hour. Then, chloroformwas added to the reaction mixture, and extracted. The organic layer wasdried by anhydrous sodium salfate, and concentrated. The residue obtaindwas subjected to silica gel column chromatography to obtain 3.51 g of3-benzyloxymethylthio-5-chloro-1,2,4-thiadiazole.3-benzyloxymethylthio-5-chloro-1,2,4-thiadiazole

¹H-NMR:7.36-7.28 (m, 5H)5.45 (s, 2H)4.69 (s, 2H)

Next, formulation examples will be described below. Parts representparts by weight.

FORMULATION EXAMPLE 1

9 parts of each of the compounds of the present invention 1 to 23 isdissolved in 37.5 parts of xylene and 37.5 parts ofN,N-dimethylformamide, and 10 parts of polyoxyethylene styryl phenylether and 6 parts of calcium dodecylbenzenesulfonate are added thereto,followed by well stirring and mixing, to give a emulsifiable concentratefor each compound.

FORMULATION EXAMPLE 2

9 parts of each of the compounds of the present invention 1 to 23 isadded to a mixture containing 4 parts of sodium laurylsulfate, 2 partsof calcium lignin sulfonate, 20 parts of synthetic hydrated siliconeoxide fine powder, and 65 parts of diatomaceous earth, followed by wellstirring and mixing, to give a wettable powder for each compound.

FORMULATION EXAMPLE 3

To 3 parts of each of the compounds of the present invention 1 to 23 areadded 5 part of synthetic hydrated silicon oxide fine powder, 5 parts ofsodium dodecylbenzenesulfonate, 30 parts of bentonite, and 57 parts ofclay, followed by well stirring and mixing, and an appropriate amount ofwater is added to this mixture, followed by further stirring,granulation with a granulator, and air drying, to give a granule foreach compound.

FORMULATION EXAMPLE 4

4.5 parts of each of the compounds of the present invention 1 to 23, 1part of synthetic hydrated silicon oxide fine powder, 1 part of DRILESSB (manufactured by Sankyo Co., Ltd.) as a coagulant and 7 parts of clayare mixed thoroughly in a mortar, then, stirred to mix by a juice mixer.To the resulted mixture is added 86.5 parts of cut clay, they weresufficiently stirred to mix, to obtain a dust for each compound.

FORMULATION EXAMPLE 5

10 parts of each of the compounds of the present invention 1 to 23, 35parts of white carbon containing 50 parts of polyoxyethylene alkyl ethersulfate ammonium salt, and 55 parts of water are mixed and pulverized bythe wet grinding method to give a formulation for each compound.

FORMULATION EXAMPLE 6

0.5 part of each of the compounds of the present invention 1 to 23 isdissolved in a 10 parts of dichloromethane, and the resulting solutionis mixed with 89.5 parts of Isper M (isoparafin; trademark of ExxonChemical) to give an oil solution for each compound.

FORMULATION EXAMPLE 7

An aerosol vessel is filled with 0.1 part of each of the compounds ofthe present invention 1 to 23 and 49.9 parts of Noethiozol (manufacturedby Chuo Kasei Co.). Then, the vessel is equipped with an aerosol valve,25 parts of dimethylether and 25 parts of liquefied petroleum gas arecharged into the aerosol vessel is shaken and equipped with an actuator,to give an oil-based aerosol.

FORMULATION EXAMPLE 8

An aerosol vessel is filled with 0.6 part of each of the compounds ofthe present invention 1 to 23, 0.01 part of BHT, 5 parts of xylene, 3.39parts of deodorized kerosene and 1 part of an emulsifiable agent (Atmos300, trademark of Atmos Chemicals Co.), and 50 parts of water. Then, thevessel is equipped with a valve and 40 parts of a propellant (LPG) ischarged through the valve into the aerosol vessel under pressure, togive a water-based aerosol.

Continuously, it is shown by a Test Example that the compound of thepresent invention is useful as an active ingredient of an arthropodpests controlling composition.

TEST EXAMPLE

Each formulation on the test compounds obtained according to theFormulation Example 5 was diluted with water so that the activeingredient concentration came to 500 ppm to prepare a diluting liquid.

The seeds of cucumber were planted in polyethylene cups and grown untiltheir first foliage leaves developed, on which about 20 cotton aphids(Aphis gossypii) were made parasitic. After one day, the diluting liquiddescribed above was sprayed at the rate of 20 ml/cup onto the cucumberplants. On 6 day after application, the number of cotton aphids (Aphisgossypii) was examined.

As a result, in the treatment of the compound of the present invention 1to 9, 11, 13 to 15, 17 to 23, the numbers of the living cotton aphids(Aphis gossypii) were three or less. On the other hand, in thenon-treatment, the number of the living cotton aphids (Aphis gossypii)was twenty or more.

INDUSTRIAL APPLICABILITY

By using the compound of the present invention, arthropod pests can becontrolled.

1. A thiadiazole compound of the formula (A):

wherein, in the formula, R¹ represents a C1-C7 alkyl group, a C3-C7alkenyl group, a C3-C7 alkynyl group, a C2-C7 alkoxyalkyl group, a C2-C7alkylthioalkyl group, a C4-C7 alkoxyalkoxyalkyl group, a C4-C7alkylthioalkoxyalkyl group, a phenyl group in which the phenyl group maybe substituted, a C1-C2 alkyl group substituted with a phenyl group inwhich the phenyl group may be substituted, a C1-C2 alkyl groupsubstituted with a phenoxy group in which the phenoxy group may besubstituted, a C2-C3 alkoxyalkyl group substituted with a phenyl groupin which the phenyl group may be substituted, or the formula (B):

wherein R³ represents a C1-C3 alkyl group, R⁴ represents a hydrogenatom, a methyl group, an ethyl group, a propyl group, or a phenyl groupin which the phenyl group may be substituted; and R² represents a C1-C4alkyl group substituted with a hetero ring group in which the heteroring group may be substituted, which the hetero ring group is afive-membered ring containing only an oxygen atom(s) or a sulfur atom(s)as a hetero atom(s).
 2. The thiadiazole compound according to claim 1,wherein R¹ is a C1-C7 alkyl group in the formula (A).
 3. The thiadiazolecompound according to claim 1, wherein R¹ is a C3-C7 alkenyl group, aC2-C7 alkoxyalkyl group, a C2-C7 alkylthioalkyl group, a C4-C7alkoxyalkoxyalkyl group, or a C4-C7 alkylthioalkoxyalkyl group in theformula (A).
 4. The thiadiazole compound according to claim 1, whereinR¹ is a phenyl group in which the phenyl group may be substituted withone or more selected from the Substituent Group A described below, aC1-C2 alkyl group substituted with a phenyl group in which the phenylgroup may be substituted with one or more selected from the SubstituentGroup A described below, a C1-C2 alkyl group substituted with aphenyloxy group in which the phenyloxy group may be substituted with oneor more selected from the Substituent Group A described below, or aC2-C3 alkoxyalkyl group substituted with a phenyl group in which thephenyl group may be substituted with one or more selected from theSubstituent Group A described below in the formula (A). SubstituentGroup A C1-C4 alkyl group, C1-C4 haloalkyl group, C1-C4 alkoxy group,C1-C4 alkylthio group, C1-C4 haloalkoxy group, nitro group, cyano group,and halogen atoms
 5. The thiadiazole compound according to claim 1,wherein R¹ is the formula (B):

wherein R³ represents a C1-C3 alkyl group, and R⁴ represents a hydrogenatom, a methyl group, a ethyl group, or a phenyl group in which thephenyl group may be substituted with one or more selected from the groupconsisting of C1-C4 alkyl group, C1-C4 haloalkyl group, C1-C4 alkoxygroup, C1-C4 alkylthio group, C1-C4 haloalkoxy group, nitro group, cyanogroup, and halogen atoms; in the formula (A).
 6. The thiadiazolecompound according to claim 1, wherein R¹ is a phenyl group in which thephenyl group may be substituted with one or more selected from theSubstituent Group A described below, a benzyl group in which the benzylgroup may be substituted with one or more selected from the SubstituentGroup A described below, a phenyloxymethyl group in which thephenyloxymethyl group may be substituted with one or more selected fromthe Substituent Group A described below, or a benzyloxymethyl group inwhich the benzyloxymethyl group may be substituted with one or moreselected from the Substituent Group A described below in the formula(A). Substituent Group A C1-C4 alkyl group, C1-C4 haloalkyl group, C1-C4alkoxy group, C1-C4 alkylthio group, C1-C4 haloalkoxy group, nitrogroup, cyano group, and halogen atoms
 7. The thiadiazole compoundaccording to claim 1, wherein R² is a C1-C4 alkyl group substituted withhetero ring group in which the hetero ring group may be substituted withone or more selected from the Substituent Group B described below, whichthe hetero ring group is a five-membered ring containing only an oxygenatom(s) or a sulfur atom(s) as a hetero atom(s) in the formula (A).Substituent Group B C1-C4 alkyl group, halogen atoms, trifluoromethylgroup, formyl group, and nitro group
 8. The thiadiazole compoundaccording to claim 1, wherein R² is a C1-C4 alkyl group substituted withhetero ring group in which the hetero ring group may be substituted withone or more selected from the Substituent Group B described below, whichthe hetero ring group is a five-membered ring containing only an oxygenatom(s) as a hetero atom(s) in the formula (A). Group B C1-C4 alkylgroup, halogen atoms, trifluoromethyl group, formyl group, and nitrogroup
 9. A arthropod pests controlling composition comprising aneffective amount of the thiadiazole compound according to claim
 1. 10. Amethod for controlling arthropod pests comprising applying an effectiveamount of the thiadiazole compound according to claim 1 to arthropodpests or habitat arthropod pests.
 11. Use of the thiadiazole compoundaccording to claim 1 as arthropod pests controlling composition.